Vinyl terminated higher olefin copolymers and methods to produce thereof

ABSTRACT

This invention relates to a vinyl terminated higher olefin copolymer having an Mn of 300 g/mol or more (measured by  1 H NMR) comprising: (i) from about 20 to about 99.9 mol % of at least one C 5  to C 40  higher olefin monomer; and (ii) from about 0.1 to about 80 mol % of propylene; wherein the higher olefin copolymer has at least 40% allyl chain ends. The copolymer may also have an isobutyl chain end to allyl chain end ratio of less than 0.7:1 and/or an allyl chain end to vinylidene chain end ratio of greater than 2:1.

STATEMENT OF RELATED CASES

This application is related to U.S. Ser. No. 12/143,663, filed on Jun.20, 2008 (Published as WO 2009/155471); U.S. Ser. No. 12/487,739, filedon Jun. 19, 2009 (Published as WO 2009/155472); U.S. Ser. No.12/488,066, filed on Jun. 19, 2009 (Published as WO 2009/155510); Ser.No. 12/488,093, filed on Jun. 19, 2009 (Published as WO 2009/155517);and U.S. Ser. No. 12/642,453, filed Dec. 18, 2009; which is acontinuation-in-part application of U.S. Ser. No. 12/533,465, filed onJul. 31, 2009, which claims priority to and the benefit of U.S. Ser. No.61/136,172, filed on Aug. 15, 2008; which are all incorporated byreference herein.

This invention also relates to the following concurrently filedapplications:

a) U.S. Ser. No. 13/072,280, filed Mar. 25, 2011, entitled “NovelCatalysts and Methods of Use Thereof to Produce Vinyl TerminatedPolymers”;

b) U.S. Ser. No. 13/072,189, filed Mar. 25, 2011, entitled “AmineFunctionalized Polyolefin and Methods for Preparation Thereof “;

c) U.S. Ser. No. 13/072,279, filed Mar. 25, 2011, entitled “EnhancedCatalyst Performance for Production of Vinyl Terminated Propylene andEthylene/Propylene Macromers “;

d) U.S. Ser. No. 13/072,383, filed Mar. 25, 2011, entitled “DiblockCopolymers Prepared by Cross Metathesis”;

e) U.S. Ser. No. 13/072,261, filed Mar. 25, 2011, entitled “AmphiphilicBlock Polymers Prepared by Alkene Metathesis”;

f) U.S. Ser. No. 13/072,288, filed Mar. 25, 2011, entitled “VinylTerminated Higher Olefin Polymers and Methods to Produce Thereof”;

g) U.S. Ser. No. 13/072,305, filed Mar. 25, 2011, entitled“Hydrosilyation of Vinyl T-efminated-Macromers with Metallocenes”;

h) U.S. Ser. No. 13/072,432, filed Mar. 25, 2011, entitled “OlefinTriblock Polymers via Ring-Opening Metathesis Polymerization”;

i) U.S. Ser. No. 13/072,330, filed Mar. 25, 2011, entitled “BlockCopolymers from Silylated Vinyl Terminated Macromers”; and

j) U.S. Ser. No. 61/467,681, filed Mar. 25, 2011, entitled “BranchedVinyl Terminated Polymers and Methods for Production Thereof”.

FIELD OF THE INVENTION

This invention relates to olefin copolymerization, particularly toproduce vinyl terminated copolymers.

BACKGROUND OF THE INVENTION

Alpha-olefins, especially those containing about 6 to about 20 carbonatoms, have been used as intermediates in the manufacture of detergentsor other types of commercial products. Such alpha-olefins have also beenused as comonomers, especially in linear low density polyethylene.Commercially produced alpha-olefins are typically made by oligomerizingethylene. Longer chain alpha-olefins, such as vinyl-terminatedpolyethylenes, are also known and can be useful as building blocksfollowing functionalization or as macromonomers.

Allyl terminated low molecular weight solids and liquids of ethylene orpropylene have also been produced, typically for use as branches inpolymerization reactions. See, for example, Rulhoff, Sascha andKaminsky, (“Synthesis and Characterization of Defined BranchedPoly(propylene)s with Different Microstructures by Copolymerization ofPropylene and Linear Ethylene Oligomers (C_(n)=26-28) withMetallocenes/MAO Catalysts,” Macromolecules, 16, 2006, pp. 1450-1460),and Kaneyoshi, Hiromu et al. (“Synthesis of Block and Graft Copolymerswith Linear Polyethylene Segments by Combination of DegenerativeTransfer Coordination Polymerization and Atom Transfer RadicalPolymerization,” Macromolecules, 38, 2005, pp. 5425-5435).

Further, U.S. Pat. No. 4,814,540 discloses bis(pentamethylcyclopentadienyl) hafnium dichloride, bis(pentamethyl cyclopentadienyl)zirconium dichloride and bis(tetramethyl n-butyl cyclopentadienyl)hafnium dichloride with methylalumoxane in toluene or hexane with orwithout hydrogen to make allylic vinyl terminated propylenehomo-oligomers having a low degree of polymerization of 2-10. Theseoligomers do not have high Mn's and do not have at least 93% allylicvinyl unsaturation. Likewise, these oligomers lack comonomer and areproduced at low productivities with a large excess of alumoxane (molarratio≧600 Al/M; M=Zr, Hf). Additionally, no less than 60 wt % solvent(solvent+propylene basis) is present in all of the examples.

Teuben et al. (J. Mol. Catal., 62, 1990, pp. 277-287) discloses the useof [Cp*₂MMe(THT)]+[BPh₄] (M=Zr and Hf; Cp*=pentamethylcyclopentadienyl;Me=methyl, Ph=phenyl; THT=tetrahydrothiophene), to make propyleneoligomers. For M=Zr, a broad product distribution with oligomers up toC₂₄ (number average molecular weight (Mn) of 336) was obtained at roomtemperature. Whereas, for M=Hf, only the dimer 4-methyl-1-pentene andthe trimer 4,6-dimethyl-1-heptene were formed. The dominant terminationmechanism appeared to be beta-methyl transfer from the growing chainback to the metal center, as was demonstrated by deuterium labelingstudies.

X. Yang et al. (Angew. Chem. Intl. Ed. Engl., 31, 1992, pg. 1375)discloses amorphous, low molecular weight polypropylene made at lowtemperatures where the reactions showed low activity and product having90% allylic vinyls, relative to all unsaturations, by ¹H NMR.Thereafter, Resconi et al. (J. Am. Chem. Soc., 114, 1992, pp.1025-1032), discloses the use ofbis(pentamethylcyclopentadienyl)zirconium andbis(pentamethylcyclopentadienyl)hafnium to polymerize propylene andobtained beta-methyl termination resulting in oligomers and lowmolecular weight polymers with “mainly allyl- and iso-butyl-terminated”chains. As is the case in U.S. Pat. No. 4,814,540, the oligomersproduced do not have at least 93% allyl chain ends, an Mn of about 500to about 20,000 g/mol (as measured by ¹H NMR), and the catalyst has lowproductivity (1-12,620 g/mmol metallocene/hr; >3000 wppm Al inproducts).

Similarly, Small and Brookhart, (Macromolecules, 32, 1999, pg. 2322)disclose the use of a pyridylbisamido iron catalyst in a low temperaturepolymerization to produce low molecular weight amorphous propylenematerials apparently having predominant or exclusive 2,1 chain growth,chain termination via beta-hydride elimination, and high amounts ofvinyl end groups.

Weng et al. (Macromol Rapid Comm. 2000, 21, pp. 1103-1107) disclosesmaterials with up to about 81 percent vinyl termination made usingdimethylsilyl bis(2-methyl,4-phenyl-indenyl) zirconium dichloride andmethylalumoxane in toluene at about 120° C. The materials have a Mn ofabout 12,300 (measured with ¹H NMR) and a melting point of about 143° C.

Macromolecules, 33, 2000, pp. 8541-8548 discloses preparation ofbranch-block ethylene-butene polymer made by reincorporation of vinylterminated polyethylene, said branch-block polymer made by a combinationof Cp₂ZrCL₂ and (C₅Me₄SiMe₂NC₁₂H₂₃)TiCl₂ activated with methylalumoxane.

Moscardi et al. (Organometallics, 20, 2001, pg. 1918) discloses the useof rac-dimethylsilylmethylenebis(3-t-butyl indenyl)zirconium dichloridewith methylalumoxane in batch polymerizations of propylene to producematerials where “ . . . allyl end group always prevails over any otherend groups, at any [propene].” In these reactions, morphology controlwas limited and approximately 60% of the chain ends are allylic.

Coates et al. (Macromolecules, 38, 2005, pg. 6259) discloses preparationof low molecular weight syndiotactic polypropylene ([rrrr]=0.46-0.93)with about 100% allyl end groups using bis(phenoxyimine)titaniumdichloride ((PHI)₂TiCl₂) activated with modified methyl alumoxane (MMAO;Al/Ti molar ratio=200) in batch polymerizations run between −20° C. and+20° C. for four hours. For these polymerizations, propylene wasdissolved in toluene to create a 1.65 M toluene solution. Catalystproductivity was very low (0.95 to 1.14 g/mmol Ti/hr).

JP 2005-336092 A2 discloses the manufacture of vinyl-terminatedpropylene polymers using materials such as H₂SO₄ treatedmontmorillonite, triethylaluminum, triisopropyl aluminum, where theliquid propylene is fed into a catalyst slurry in toluene. This processproduces substantially isotactic macromonomers that do not have asignificant amount of amorphous material.

Rose et al. (Macromolecules, 41, 2008, pp. 559-567) disclosespoly(ethylene-co-propylene) macromonomers not having significant amountsof iso-butyl chain ends. Those were made with bis(phenoxyimine) titaniumdichloride ((PHI)₂TiCl₂) activated with modified methylalumoxane (MMAO;Al/Ti molar ratio range 150 to 292) in semi-batch polymerizations (30psi propylene added to toluene at 0° C. for 30 min, followed by ethylenegas flow at 32 psi of over-pressure at about 0° C. for polymerizationtimes of 2.3 to 4 hours to produce E-P copolymer having an Mn of about4,800 to 23,300. In four reported copolymerizations, allylic chain endsdecreased with increasing ethylene incorporation roughly according tothe equation:% allylic chain ends (of total unsaturations)=−0.95 (mol % ethyleneincorporated)+100.For example, 65% allyl (compared to total unsaturation) was reported forE-P copolymer containing 29 mol % ethylene. This is the highest allylpopulation achieved. For 64 mol % incorporated ethylene, only 42% of theunsaturations are allylic. Productivity of these polymerizations rangedfrom 0.78×10² g/mmol Ti/hr to 4.62×10² g/mmol Ti/hr.

Prior to this work, Zhu et al. reported only low (−38%) vinyl terminatedethylene-propylene copolymer made with the constrained geometrymetallocene catalyst [C₅Me₄(SiMe₂N-tert-butyl)TiMe₂ activated withB(C₆F₅)₃ and MMAO (Macromolecules, 35, 2002, pp. 10062-10070 andMacromolecules Rap. Commun., 24, 2003, pp. 311-315).

Janiak and Blank summarize a variety of work related to oligomerizationof olefins (Macromol. Symp., 236, 2006, pp. 14-22).

However, higher olefin copolymerizations to produce allyl terminatedhigher olefin copolymers are not known. Accordingly, there is a need fornew catalysts that produce allyl terminated higher olefin copolymers,particularly in high yields, with a wide range of molecular weight, andwith high catalyst activity. Further, there is a need for higher olefincopolymers macromonomers that have allyl termination present in highamounts (40% or more), with control over a wide range of molecularweights that can be made at commercial temperatures and which can bemade at commercial rates (5,000 g/mmol/hr productivity or more).Further, there is a need for higher olefin copolymer reactive materialshaving allyl termination which can be functionalized and used inadditive applications, or as macromonomers for the synthesis ofpoly(macromonomers).

SUMMARY OF THE INVENTION

This invention relates to higher olefin copolymers having an Mn(measured by ¹H NMR) of 300 g/mol or greater (preferably 300 to 60,000g/mol) comprising: (i) from about 20 to 99.9 mol % of at least one C₅ toC₄₀ higher olefin; and (ii) from about 0.1 to 80 mol % of propylene;wherein the higher olefin copolymer has at least 40% allyl chain ends.

This invention relates to higher olefin copolymers having an Mn(measured by ¹H NMR) of 300 g/mol or greater (preferably 300 to 60,000g/mol) comprising: (i) from about 80 to 99.9 mol % of at least one C₄olefin; and (ii) from about 0.1 to 20 mol % of propylene; wherein thehigher olefin copolymer has at least 40% allyl chain ends.

This invention also relates to a process for making higher olefincopolymers, wherein the process comprises contacting, underpolymerization conditions: (i) 20 to 99.9 mol % of at least one C₅ toC₄₀ higher olefin; and (ii) 0.1 to 80 mol % of propylene; wherein thecontacting occurs in the presence of a catalyst system comprising anactivator and at least one metallocene compound represented by at leastone of the formulae:

where M is hafnium or zirconium; each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system); each Q is,independently carbon or a heteroatom; each R¹ is, independently, a C₁ toC₈ alkyl group, R¹ may the same or different as R²; each R² is,independently, a C₁ to C₈ alkyl group; each R³ is, independently,hydrogen, or a substituted or unsubstituted hydrocarbyl group havingfrom 1 to 8 carbon atoms, provided however that at least three R³ groupsare not hydrogen; each

R⁴ is, independently, hydrogen or a substituted or unsubstitutedhydrocarbyl group, a heteroatom or heteroatom containing group; R⁵ ishydrogen or a C₁ to C₈ alkyl group; R⁶ is hydrogen or a C₁ to C₈ alkylgroup; each R⁷ is, independently, hydrogen, or a C₁ to C₈ alkyl group,provided however that at least seven R⁷ groups are not hydrogen; R₂^(a)T is a bridging group where T is a group 14 element (preferably C,Si, or Ge, preferably Si) and each R^(a) is, independently, hydrogen,halogen or a C₁ to C₂₀ hydrocarbyl, and two R^(a) can form a cyclicstructure including aromatic, partially saturated, or saturated cyclicor fused ring system; and further provided that any two adjacent Rgroups may form a fused ring or multicenter fused ring system where therings may be aromatic, partially saturated or saturated;

where M is hafnium or zirconium; each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system); each R⁸ is,independently, a C₁ to C₁₀ alkyl group; each R⁹ is, independently, a C₁to C₁₀ alkyl group; each R¹⁰ is hydrogen; each R¹¹, R¹², and R¹³, is,independently, hydrogen or a substituted or unsubstituted hydrocarbylgroup, a heteroatom or heteroatom containing group; T is a bridginggroup; and further provided that any of adjacent R¹¹, R¹², and R¹³groups may form a fused ring or multicenter fused ring system where therings may be aromatic, partially saturated or saturated;

wherein M is hafnium or zirconium; each X is, independently, selectedfrom the group consisting of hydrocarbyl radicals having from 1 to 20carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halogens, dienes, amines, phosphines, ethers, or a combination thereof;each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group; and eachR¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ are,independently, hydrogen, or a substituted or unsubstituted hydrocarbylgroup having from 1 to 8 carbon atoms.

This invention also relates to a process for making higher olefincopolymers, wherein the process comprises contacting, underpolymerization conditions: (i) 80 to 99.9 mol % of at least one C₄olefin; and (ii) 0.1 to 20 mol % of propylene; wherein the contactingoccurs in the presence of a catalyst system comprising an activator andat least one metallocene compound represented by at least one of theformulae:

where M is hafnium or zirconium; each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system); each Q is,independently carbon or a heteroatom; each R¹ is, independently, a C₁ toC₈ alkyl group, R¹ may the same or different as R²; each R² is,independently, a C₁ to C₈ alkyl group; each R³ is, independently,hydrogen, or a substituted or unsubstituted hydrocarbyl group havingfrom 1 to 8 carbon atoms, provided however that at least three R³ groupsare not hydrogen; each R⁴ is, independently, hydrogen or a substitutedor unsubstituted hydrocarbyl group, a heteroatom or heteroatomcontaining group; R⁵ is hydrogen or a C₁ to C₈ alkyl group; R⁶ ishydrogen or a C₁ to C₈ alkyl group; each R⁷ is, independently, hydrogen,or a C₁ to C₈ alkyl group, provided however that at least seven R⁷groups are not hydrogen; R₂ ^(a)T is a bridging group where T is a group14 element (preferably C, Si, or Ge, preferably Si); and each R^(a) is,independently, hydrogen, halogen or a C₁ to C₂₀ hydrocarbyl, and twoR^(a) can form a cyclic structure including aromatic, partiallysaturated or saturated cyclic or fused ring system; and further providedthat any two adjacent R groups may form a fused ring or multicenterfused ring system where the rings may be aromatic, partially saturatedor saturated;

where M is hafnium or zirconium; each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system); each R⁸ is,independently, a C₁ to C₁₀ alkyl group; each R⁹ is, independently, a C₁to C₁₀ alkyl group; each R¹⁰ is hydrogen; each R¹¹, R¹², and R¹³, is,independently, hydrogen or a substituted or unsubstituted hydrocarbylgroup, a heteroatom or heteroatom containing group; T is a bridginggroup (such as R₂ ^(a)T as defined above); and further provided that anyof adjacent R¹¹, R¹², and R¹³ groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated;

wherein M is hafnium or zirconium; each X is, independently, selectedfrom the group consisting of hydrocarbyl radicals having from 1 to 20carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halogens, dienes, amines, phosphines, ethers, or a combination thereof;each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group; and eachR¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ are,independently, hydrogen, or a substituted or unsubstituted hydrocarbylgroup having from 1 to 8 carbon atoms.

This invention even further relates to a composition comprising a higherolefin copolymer having an Mn (measured by ¹H NMR) of greater than 200g/mol comprising: (i) from about 20 to 99.9 mol % of at least one C₅ toC₄₀ higher olefin; and (ii) from about 0.1 to 80 mol % of propylene;wherein the higher olefin copolymer has at least 40% allyl chain ends.

This invention even further relates to a composition comprising a higherolefin copolymer having an Mn (measured by ¹H NMR) of greater than 200g/mol comprising: (i) from about 80 to 99.9 mol % of at least one C₄olefin; and (ii) from about 0.1 to 20 mol % of propylene; wherein thehigher olefin copolymer has at least 40% allyl chain ends.

The invention yet further relates to the use of the compositionsdisclosed herein as lubricants.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of viscosity as a function of temperature forrepresentative allyl terminated hexene-propylene copolymers as comparedto allyl terminated propylene homopolymers.

DETAILED DESCRIPTION

The inventors have surprisingly discovered a new class of vinylterminated polymers. Described herein are vinyl terminated higher olefincopolymers, processes to produce such vinyl terminated higher olefincopolymers, and compositions comprising vinyl terminated higher olefincopolymers. These vinyl terminated higher olefin copolymers may findutility as macromonomers for the synthesis of poly(macromonomers), blockcopolymers, and as additives, for example, as additives to lubricants.Advantageously, the vinyl group of these vinyl terminated copolymersprovides a path to functionalization. These functionalized copolymersmay be also useful as additives, such as in lubricants.

As used herein, “molecular weight” means number average molecular weight(Mn), unless otherwise stated.

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as in CHEMICALAND ENGINEERING NEWS, 63(5), pg. 27 (1985). Therefore, a “Group 4 metal”is an element from Group 4 of the Periodic Table.

“Catalyst activity” is a measure of how many grams of polymer (P) areproduced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹hr⁻¹.“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹hr⁻¹.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, including, but not limited to ethylene, propylene, and butene,the olefin present in such polymer or copolymer is the polymerized formof the olefin. For example, when a copolymer is said to have an“ethylene” content of 35 wt % to 55 wt %, it is understood that the merunit in the copolymer is derived from ethylene in the polymerizationreaction and said derived units are present at 35 wt % to 55 wt %, basedupon the weight of the copolymer. A “polymer” has two or more of thesame or different mer units. The term “polymer,” as used herein,includes oligomers (up to 100 mer units), and larger polymers (greaterthan 100 mer units). A “homopolymer” is a polymer having mer units thatare the same. A “copolymer” is a polymer having two or more mer unitsthat are different from each other. A “terpolymer” is a polymer havingthree mer units that are different from each other. “Different” as usedto refer to mer units indicates that the mer units differ from eachother by at least one atom or are different isomerically. Accordingly,the definition of copolymer, as used herein, includes terpolymers andthe like.

“Higher olefin,” as used herein, means C₄ to C₄₀ olefins; preferably C₅to C₃₀ α-olefins; more preferably C₅-C₂₀ α-olefins; or even morepreferably, C₅-C₁₂ α-olefins. A “higher olefin copolymer” is a polymercomprising two or more different monomer units (where different meansthe monomer units differ by at least one atom), at least one of which isa higher olefin monomer unit.

As used herein, Mn is number average molecular weight (measured by ¹HNMR, unless stated otherwise), Mw is weight average molecular weight(measured by Gel Permeation Chromatography, GPC), and Mz is z averagemolecular weight (measured by GPC), wt % is weight percent, mol % ismole percent, vol % is volume percent and mol is mole. Molecular weightdistribution (MWD) is defined to be Mw (measured by GPC) divided by Mn(measured by GPC), Mw/Mn. Unless otherwise noted, all molecular weights(e.g., Mw, Mn, Mz) have units of g/mol.

Vinyl Terminated Copolymers

In a preferred embodiment, the vinyl terminated higher olefin (VT-HO)copolymers described herein have an Mn (measured by ¹H NMR) of greaterthan 200 g/mol (preferably 300 to 60,000 g/mol, 400 to 50,000 g/mol, 500to 35,000 g/mol, 300 to 15,000 g/mol, 400 to 12,000 g/mol, or 750 to10,000 g/mol), and comprise: (i) from about 20 to 99.9 mol % (preferablyfrom about 25 to about 90 mol %, from about 30 to about 85 mol %, fromabout 35 to about 80 mol %, from about 40 to about 75 mol %, or fromabout 50 to about 95 mol %) of at least one C₅ to C₄₀ (preferably C₆ toC₂₀) higher olefin; and (ii) from about 0.1 to 80 mol % (preferably fromabout 5 mol % to 70 mol %, from about 10 to about 65 mol %, from about15 to about 55 mol %, from about 25 to about 50 mol %, or from about 30to about 80 mol %) of propylene; wherein the VT-HO copolymer has atleast 40% allyl chain ends (preferably at least 50% allyl chain ends, atleast 60% allyl chain ends, at least 70% allyl chain ends, or at least80% allyl chain ends, at least 90% allyl chain ends, at least 95% allylchain ends) relative to total unsaturation; and, optionally, an isobutylchain end to allyl chain end ratio of less than 0.70:1, less than0.65:1, less than 0.60:1, less than 0.50:1, or less than 0.25:1, andfurther optionally, an allyl chain end to vinylidene chain end ratio ofgreater than 2:1 (preferably greater than 2.5:1, greater than 3:1,greater than 5:1, or greater than 10:1); and even further optionally, anallyl chain end to vinylene ratio is greater than 1:1 (preferablygreater than 2:1, or greater than 5:1).

In another embodiment, the higher olefin copolymer has an Mn of 300g/mol or more (measured by ¹H NMR, preferably 300 to 60,000 g/mol, 400to 50,000 g/mol, 500 to 35,000 g/mol, 300 to 15,000 g/mol, 400 to 12,000g/mol, or 750 to 10,000 g/mol), and comprises:

-   -   (i) from about 80 to about 99.9 mol % of at least one C₄ olefin,        preferably about 85 to about 99.9 mol %, more preferably about        90 to about 99.9 mol %;    -   (ii) from about 0.1 to about 20 mol % of propylene, preferably        about 0.1 to about 15 mol %, more preferably about 0.1 to about        10 mol %; and        wherein the higher olefin copolymer has at least 40% allyl chain        ends (preferably at least 50% allyl chain ends, at least 60%        allyl chain ends, at least 70% allyl chain ends, or at least 80%        allyl chain ends, at least 90% allyl chain ends, at least 95%        allyl chain ends) relative to total unsaturation, and in some        embodiments, an isobutyl chain end to allyl chain end ratio of        less than 0.70:1, less than 0.65:1, less than 0.60:1, less than        0.50:1, or less than 0.25:1, and in further embodiments, an        allyl chain end to vinylidene group ratio of more than 2:1, more        than 2.5:1, more than 3:1, more than 5:1, or more than 10:1.

The VT-HO polymer may be a copolymer, a terpolymer, or so on.

VT-HO copolymers generally have a saturated chain end (or terminus)and/or an unsaturated chain end, or terminus. The unsaturated chain endof the inventive copolymers comprises the “allyl chain end.” An allylchain end is represented by CH₂CH—CH₂₋, as shown in formula:

where M represents the copolymer chain. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup,” and “vinyl terminated” are used interchangeably in the followingdescription.

The number of allyl chain ends, vinylidene chain ends and vinylene chainends is determined using ¹H NMR at 120° C. using deuteratedtetrachloroethane as the solvent on a at least 250 MHz NMR spectrometer,and in selected cases, confirmed by ¹³C NMR. Resconi has reported protonand carbon assignments (neat perdeuterated tetrachloroethane used forproton spectra, while a 50:50 mixture of normal and perdeuteratedtetrachloroethane was used for carbon spectra; all spectra were recordedat 100° C. on a Bruker spectrometer operating at 500 MHz for proton and125 MHz for carbon) for vinyl terminated propylene oligomers in J.American Chemical Soc., 114, 1992, pp. 1025-1032 that are useful herein.Allyl chain ends are reported as a molar percentage of the total numberof moles of unsaturated groups (that is, the sum of allyl chain ends,vinylidene chain ends, vinylene chain ends, and the like).

In another embodiment, any of the vinyl terminated polyolefins describedor useful herein have 3-alkyl vinyl end groups (where the alkyl is a C₁to C₃₈ alkyl), also referred to as a “3-alkyl chain ends” or a “3-alkylvinyl termination”, represented by the formula:

where “••••” represents the polyolefin chain and R^(b) is a C₁ to C₃₈alkyl group, preferably a C₁ to C₂₀ alkyl group, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,docecyl, and the like. The amount of 3-alkyl chain ends is determinedusing ¹³C NMR as set out below.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% 3-alkyl chain ends(preferably at least 10% 3-alkyl chain ends, at least 20% 3-alkyl chainends, at least 30% 3-alkyl chain ends; at least 40% 3-alkyl chain ends,at least 50% 3-alkyl chain ends, at least 60% 3-alkyl chain ends, atleast 70% 3-alkyl chain ends; at least 80% 3-alkyl chain ends, at least90% 3-alkyl chain ends; at least 95% 3-alkyl chain ends, relative tototal unsaturations.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% 3-alkyl+allyl chain ends,(e.g., all 3-alkyl chain ends plus all allyl chain ends), preferably atleast 10% 3-alkyl+allyl chain ends, at least 20% 3-alkyl+allyl chainends, at least 30% 3-alkyl+allyl chain ends; at least 40% 3-alkyl+allylchain ends, at least 50% 3-alkyl+allyl chain ends, at least 60%3-alkyl+allyl chain ends, at least 70% 3-alkyl+allyl chain ends; atleast 80% 3-alkyl+allyl chain ends, at least 90% 3-alkyl+allyl chainends; at least 95% 3-alkyl+allyl chain ends, relative to totalunsaturations.

In some embodiments, the VT-HO copolymer has at least 40% allyl chainends (at least 50% allyl chain ends, at least 60% allyl chain ends, atleast 70% allyl chain ends, at least 80% allyl chain ends, at least 90%allyl chain ends, or at least 95% allyl chain ends).

In another embodiment, any of the vinyl terminated polyolefins describedor useful herein have 3-alkyl vinyl end groups (where the alkyl is a C₁to C₃₈ alkyl), also referred to as “3-alkyl chain ends” or “3-alkylvinyl terminations,” represented by the formula:

where “••••” represents the polyolefin chain and R^(b) is a C₁ to C₃₈alkyl group, preferably a C₁ to C₂₀ alkyl group, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,docecyl, and the like. The number of 3-alkyl chain ends is determinedusing ¹³C NMR as set out below.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% 3-alkyl chain ends(preferably at least 10% 3-alkyl chain ends, at least 20% 3-alkyl chainends, at least 30% 3-alkyl chain ends; at least 40% 3-alkyl chain ends,at least 50% 3-alkyl chain ends, at least 60% 3-alkyl chain ends, atleast 70% 3-alkyl chain ends; at least 80% 3-alkyl chain ends, at least90% 3-alkyl chain ends; at least 95% 3-alkyl chain ends, relative tototal unsaturations.

In a preferred embodiment, any of the vinyl terminated polyolefinsdescribed or useful herein have at least 5% 3-alkyl+allyl chain ends,(e.g., all 3-alkyl chain ends plus all allyl chain ends), preferably atleast 10% 3-alkyl+allyl chain ends, at least 20% 3-alkyl+allyl chainends, at least 30% 3-alkyl+allyl chain ends; at least 40% 3-alkyl+allylchain ends, at least 50% 3-alkyl+allyl chain ends, at least 60%3-alkyl+allyl chain ends, at least 70% 3-alkyl+allyl chain ends; atleast 80% 3-alkyl+allyl chain ends, at least 90% 3-alkyl+allyl chainends; at least 95% 3-alkyl+allyl chain ends, relative to totalunsaturations.

The “allyl chain end to vinylidene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylidene chain ends. In some embodiments, the allyl chain end tovinylidene chain end ratio is more than 2:1 (preferably more than 2.5:1,more than 3:1, more than 5:1, or more than 10:1). In some embodiments,the allyl chain end to vinylidene chain end ratio is in the range offrom about 10:1 to about 2:1 (preferably from about 5:1 to about 2:1 orfrom 10:1 to about 2.5:1).

The “allyl chain end to vinylene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylene chain ends. In some embodiments, the allyl chain end tovinylene ratio is greater than 1:1 (preferably greater than 2:1, orgreater than 5:1).

VT-HO copolymers also have a saturated chain end which may comprise anisobutyl chain end or a higher olefin chain end. In a propylene/higherolefin copolymerization, the polymer chain may initiate growth in apropylene monomer, thereby generating an isobutyl chain saturated chainend. Alternately, the polymer chain may initiate growth in a higherolefin monomer, generating a higher olefin chain saturated end.

An “isobutyl chain end” is defined to be an end or terminus of apolymer, represented as shown in the formula below:

where M represents the polymer chain.

A “higher olefin chain end” is defined to be an end or terminus of apolymer, represented as shown in the formula below:

where M represents the polymer chain and n is an integer selected from 4to 40.

The structure of the copolymer near the saturated chain end may differ,depending on the types and amounts of monomer(s) used, and method ofinsertion during the polymerization process. In some preferredembodiments, the structure of the polymer within four carbons of theisobutyl chain end is represented by one of the following formulae:

where M represents the rest of the polymer chain and C_(m) representsthe polymerized higher olefin monomer, each C_(m) may be the same ordifferent, and where m is an integer from 2 to 38.

The percentage of isobutyl chain ends is determined using ¹³C NMR (asdescribed in the Example section) and the chemical shift assignments inResconi et al, J. Am. Chem. Soc. 114, 1992, pp. 1025-1032 for 100%propylene oligomers and reported herein for VT-HO copolymers.

The “isobutyl chain end to allyl chain end ratio” is defined to be theratio of the percentage of isobutyl chain ends to the percentage ofallyl chain ends. In some embodiments, the isobutyl chain end to allylchain end is less than 0.70:1 (preferably less than 0.65:1, less than0.60:1, less than 0.50:1, or less than 0.25:1). In some embodiments, theisobutyl chain end to allyl chain end ratio is in the range of fromabout 0.01:1 to about 0.70:1 (preferably from about 0.05:1 to about0.65:1 or from 0.1:1 to about 0.60:1).

The VT-HO copolymer preferably has a Mn, as determined by ¹H NMR, of 300g/mol or more (preferably from about 300 to 60,000 g/mol, 400 to 50,000g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000 g/mol,preferably 400 to 12,000 g/mol, or preferably 750 to 10,000 g/mol).Further, a desirable molecular weight range can be any combination ofany upper molecular weight limit with any lower molecular weight limitdescribed above. As used herein, Mn is number average molecular weight(measured by ¹H NMR, unless stated otherwise), Mw is weight averagemolecular weight (measured by Gel Permeation Chromatography, GPC), andMz is z average molecular weight (measured by GPC), and molecular weightdistribution (MWD, Mw/Mn) is defined to be Mw (measured by GPC) dividedby Mn (measured by GPC). Mn ('H NMR) is determined according to the NMRmethod described below in the Examples section. Mn may also bedetermined using a GPC-DRI method, as described below. For the purposeof the claims, Mn is determined by ¹H NMR.

In another embodiment, the VT-HO copolymers described herein have a Mw(measured using a GPC-DRI method, as described below) of 1,000 g/mol ormore (preferably from about 1,000 to about 400,000 g/mol, preferablyfrom about 2,000 to 300,000 g/mol, preferably from about 3,000 to200,000 g/mol) and/or a Mz in the range of from about 1,700 to about150,000 g/mol or preferably from about 800 to 100,000 g/mol, and/or anMw/Mn in the range of from about 1.2 to 20 (alternately from about 1.7to 10, alternately from about 1.8 to 5.5).

In particular embodiments, the VT-HO copolymer has a Mn of 300 g/mol ormore (preferably from about 300 to about 60,000 g/mol, from about 400 toabout 50,000 g/mol, from about 500 to about 35,000 g/mol, from about 300to about 15,000 g/mol, from about 400 to about 12,000 g/mol, or fromabout 750 to about 10,000 g/mol), a Mw of 1,000 or more (preferably fromabout 1,000 to about 400,000 g/mol, from about 2,000 to 300,000 g/mol,or from about 3,000 to 200,000 g/mol), and a Mz of from about 1,700 toabout 150,000 g/mol or preferably from about 800 to 100,000 g/mol.

Mn, Mw, and Mz are measured by a GPC-DRI method using a High TemperatureSize Exclusion Chromatograph (SEC (a type of Gel PermeationChromatography, GPC), either from Waters Corporation or PolymerLaboratories), equipped with a differential refractive index detector(DRI). Experimental details, are described in: T. Sun, P. Brant, R. R.Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp.6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B columns are used. The nominal flow rate is 0.5cm³/min, and the nominal injection volume is 300 μL. The varioustransfer lines, columns and differential refractometer (the DRIdetector) are contained in an oven maintained at 135° C. Solvent for theSEC experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SEC.Polymer solutions are prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities aremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/mL at room temperatureand 1.324 g/mL at 135° C. The injection concentration is from 1.0 to 2.0mg/mL, with lower concentrations being used for higher molecular weightsamples. Prior to running each sample the DRI detector and the injectorare purged. Flow rate in the apparatus is then increased to 0.5mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours beforeinjecting the first sample. The concentration, c, at each point in thechromatogram is calculated from the baseline-subtracted

DRI signal, I_(DRI), using the following equation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymersand 0.1 otherwise. Units of parameters used throughout this descriptionof the SEC method are: concentration is expressed in g/cm³, molecularweight is expressed in g/mol, and intrinsic viscosity is expressed indL/g.

In embodiments herein, the VT-HO copolymer comprises from about 20 toabout 99.9 mol % (preferably from about 25 to about 90 mol %, from about30 to about 85 mol %, from about 35 to about 80 mol %, from about 40 toabout 75 mol %, or from about 50 to about 95 mol %) of at least one(preferably two or more, three or more, four or more, and the like) C₅to C₄₀ (preferably C₅ to C₃₀, C₆ to C₂₀, or C₈ to C₁₂) higher olefinmonomers. In other embodiments, the VT-HO copolymer comprises greaterthan 20 mol % (preferably greater than 30 mol %, greater than 40 mol %,greater than 45 mol %, greater than 50 mol %, greater than 65 mol %,greater than 75 mol %, or greater than 85 mol %) of C₅ to C₄₀(preferably C₅ to C₃₀, C₆ to C₂₀, or C₈ to C₁₂) higher olefin monomer.In yet other embodiments, the VT-HO copolymer comprises less than 99.9mol % (preferably less than 85 mol %, less than 75 mol %, less than 65mol %, less than 50 mol %, less than 35 mol %, or less than 25 mol %) ofC₅ to C₄₀ higher olefin monomer.

In embodiments herein, the VT-HO copolymer comprises from about 0.1 toabout 80 mol % of propylene (preferably from about 5 mol % to about 70mol %, from about 10 to about 65 mol %, from about 15 to about 55 mol %,from about 25 to about 50 mol %, or from about 30 to about 80 mol %). Inother embodiments, the VT-HO copolymer comprises greater than 5 mol % ofpropylene (preferably greater than 10 mol %, greater than 20 mol %,greater than 35 mol %, greater than 50 mol %, greater than 65 mol %, orgreater than 75 mol %). In yet other embodiments, the VT-HO copolymercomprises less than 80 mol % of propylene (preferably less than 75 mol%, less than 70 mol %, less than 65 mol %, less than 50 mol %, less than35 mol %, less than 20 mol %, or less than 10 mol %).

VT-HO copolymers herein comprise at least one C₅ to C₄₀ higher olefinand propylene. In some embodiments, the VT-HO copolymers comprise two ormore different C₅ to C₄₀ higher olefin monomers, three or more C₅ to C₄₀different higher olefin monomers, or four or more different C₅ to C₄₀higher olefin monomer. In some embodiments, the VT-HO copolymer alsocomprises ethylene and/or butene.

In embodiments where butene is a termonomer, the higher olefin copolymerhas an Mn of 300 g/mol or more, preferably 300 to 60,000 g/mol (measuredby ¹H NMR) and comprises: (i) from about 80 to about 99.9 mol % of atleast one C₄ olefin (preferably about 85 to about 99.9 mol %, morepreferably about 90 to about 99.9 mol %); and (ii) from about 0.1 toabout 20 mol % of propylene (preferably about 0.1 to about 15 mol % orabout 0.1 to about 10 mol %); wherein the higher olefin copolymer has atleast 40% allyl chain ends (preferably at least 50% allyl chain ends, atleast 60% allyl chain ends, at least 70% allyl chain ends, or at least80% allyl chain ends); and, in some embodiments, an isobutyl chain endto allyl chain end ratio of less than 0.70:1 (preferably less than0.65:1, less than 0.60:1, less than 0.50:1, or less than 0.25:1) and infurther embodiments, an allyl chain end to vinylidene group ratio ofmore than 2:1 (preferably more than 2.5:1, more than 3:1, more than 5:1,or more than 10:1).

In a preferred embodiment, the VT-HO copolymer comprises less than 3 wt% of functional groups selected from hydroxide, aryls and substitutedaryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen,nitrogen, and carboxyl (preferably less than 2 wt %, less than 1 wt %,less than 0.5 wt %, less than 0.1 wt %, or 0 wt %), based upon theweight of the copolymer.

In another embodiment, the VT-HO copolymer comprises at least 50 wt %(preferably at least 75 wt %, preferably at least 90 wt %), based uponthe weight of the copolymer composition, of olefins having at least 36carbon atoms (preferably at least 51 carbon atoms or at least 102 carbonatoms) as measured by ¹H NMR, assuming one unsaturation per chain.

In another embodiment, the VT-HO copolymer comprises less than 20 wt %dimer and trimer (preferably less than 10 wt %, preferably less than 5wt %, more preferably less than 2 wt %, based upon the weight of thecopolymer composition), as measured by GC. “Dimer” (and “trimer”) aredefined as copolymers having two (or three) monomer units, where themonomer units may be the same or different from each other (where“different” means differing by at least one carbon). Products wereanalyzed by GC (Agilent 6890N with auto-injector) using helium as acarrier gas at 38 cm/sec. A column having a length of 60 m (J & WScientific DB-1, 60 m×0.25 mm I.D.×1.0 μm film thickness) packed with aflame ionization detector (FID), an Injector temperature of 250° C., anda Detector temperature of 250° C. were used. The sample was injectedinto the column in an oven at 70° C., then heated to 275° C. over 22minutes (ramp rate 10° C./min to 100° C., 30° C./min to 275° C., hold).An internal standard, usually the monomer, is used to derive the amountof dimer or trimer product that is obtained. Yields of dimer and trimerproduct are calculated from the data recorded on the spectrometer. Theamount of dimer or trimer product is calculated from the area under therelevant peak on the GC trace, relative to the internal standard.

In another embodiment, the VT-HO copolymer contains less than 25 ppmhafnium or zirconium, preferably less than 10 ppm hafnium or zirconium,preferably less than 5 ppm hafnium or zirconium, based on the yield ofpolymer produced and the mass of catalyst employed. ICPES (InductivelyCoupled Plasma Emission Spectrometry), which is described in J. W.Olesik, “Inductively Coupled Plasma-Optical Emission Spectroscopy,” inthe Encyclopedia of Materials Characterization, C. R. Brundle, C. A.Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann, Boston, Mass.,1992, pp. 633-644, is used to determine the amount of an element in amaterial.

In yet other embodiments, the VT-HO copolymer is a liquid at 25° C.

In another embodiment, the VT-HO copolymers described herein have amelting temperature (T_(m), DSC first melt) in the range of from 60 to130° C., alternately 50 to 100° C. In another embodiment, the copolymersdescribed herein have no detectable melting temperature by DSC followingstorage at ambient temperature (23° C.) for at least 48 hours. The VT-HOcopolymer preferably has a glass transition temperature (Tg) of lessthan 0° C. or less (as determined by Differential Scanning calorimetryas described below), preferably −10° C. or less, more preferably −20° C.or less, more preferably −30° C. or less, more preferably −50° C. orless. Melting temperature (T_(m)) and glass transition temperature (Tg)are measured using Differential Scanning calorimetry (DSC) usingcommercially available equipment such as a TA Instruments 2920 DSC.Typically, 6 to 10 mg of the sample, that has been stored at roomtemperature for at least 48 hours, is sealed in an aluminum pan andloaded into the instrument at room temperature. The sample isequilibrated at 25° C., then it is cooled at a cooling rate of 10°C./min to −80° C. The sample is held at −80° C. for 5 min and thenheated at a heating rate of 10° C./min to 25° C. The glass transitiontemperature is measured from the heating cycle. Alternatively, thesample is equilibrated at 25° C., then heated at a heating rate of 10°C./min to 150° C. The endothermic melting transition, if present, isanalyzed for onset of transition and peak temperature. The meltingtemperatures reported are the peak melting temperatures from the firstheat unless otherwise specified. For samples displaying multiple peaks,the melting point (or melting temperature) is defined to be the peakmelting temperature (i.e., associated with the largest endothermiccalorimetric response in that range of temperatures) from the DSCmelting trace.

In another embodiment, the VT-HO copolymers described herein have aviscosity at 60° C. of greater than 1,000 cP, greater than 12,000 cP, orgreater than 100,000 cP. In other embodiments, the VT-HO copolymers havea viscosity of less than 200,000 cP, less than 150,000 cP, or less than100,000 cP. Viscosity is defined as resistance to flow is measured at anelevated temperature using a Brookfield Viscometer.

In some embodiments, the VT-HO polymers are propylene/hexene copolymers,propylene/octene copolymers, propylene/decene copolymers,propylene/dodecene copolymers, propylene/hexene/octene terpolymers,propylene/hexene/decene terpolymers, propylene/hexene/dodeceneterpolymers, propylene/octene/decene terpolymers,propylene/octene/dodecene terpolymers, propylene/decene/dodeceneterpolymers, and the like.

Uses of Vinyl Terminated Higher Olefin Copolymers

The vinyl terminated polymers prepared herein may be functionalized byreacting a heteroatom containing group with the allyl group of thepolymer, with or without a catalyst. Examples include catalytichydrosilylation, hydroformylation, hydroboration, epoxidation,hydration, dihydroxylation, hydroamination, or maleation with or withoutactivators such as free radical generators (e.g., peroxides).

In some embodiments the vinyl terminated polymers produced herein arefunctionalized as described in U.S. Pat. No. 6,022,929; A. Toyota, T.Tsutsui, and N. Kashiwa, Polymer Bulletin 48, pp. 213-219, 2002; J. Am.Chem. Soc., 1990, 112, pp. 7433-7434; and U.S. Ser. No. 12/487,739,filed on Jun. 19, 2009.

The functionalized polymers can be used in oil additivation and manyother applications. Preferred uses include additives for lubricantsand/or fuels. Preferred heteroatom containing groups include, amines,aldehydes, alcohols, acids, succinic acid, maleic acid and maleicanhydride.

In particular embodiments herein, the vinyl terminated polymersdisclosed herein, or functionalized analogs thereof, are useful asadditives. In some embodiments, the vinyl terminated polymers disclosedherein, or functionalized analogs thereof, are useful as additives to alubricant. Particular embodiments, relate to a lubricant comprising thevinyl terminated polymers disclosed herein, or functionalized analogsthereof.

In other embodiments, the vinyl terminated polymers disclosed herein maybe used as monomers for the preparation of polymer products. Processesthat may be used for the preparation of these polymer products includecoordinative polymerization and acid-catalyzed polymerization. In someembodiments, the polymeric products may be homopolymers. For example, ifa vinyl terminated polymer (A) were used as a monomer, it is possible toform a homopolymer product with the formulation (A)_(n), where n is thedegree of polymerization.

In other embodiments, the polymer products formed from mixtures ofmonomer vinyl terminated polymers may be mixed polymers, comprising twoor more repeating units that are different from each. For example, if avinyl terminated polymer (A) and a different vinyl terminated polymer(B) were copolymerized, it is possible to form a mixed polymer productwith the formulation (A)_(n)(B)_(m), where n is the number of molarequivalents of vinyl terminated polymer (A) and m is the number of molarequivalents of vinyl terminated polymer (B) that are present in themixed polymer product.

In yet other embodiments, polymer products may be formed from mixturesof the vinyl terminated polymer with another alkene. For example, if avinyl terminated polymer (A) and alkene (B) were copolymerized, it ispossible to form a mixed polymer product with the formulation(A)_(n)(B)_(m), where n is the number of molar equivalents of vinylterminated polymer and m is the number of molar equivalents of alkenethat are present in the mixed polymer product.

In particular embodiments herein, the invention relates to a compositioncomprising VT-HO copolymers having an Mn of 300 g/mol or more,preferably of 300 to 60,000 g/mol (measured by ¹H NMR), 400 to 50,000g/mol, preferably 500 to 35,000 g/mol, preferably 300 to 15,000 g/mol,preferably 400 to 12,000 g/mol, or preferably 750 to 10,000 g/mol,comprising: (i) from about 20 to 99.9 mol % of at least one C₅ to C₄₀higher olefin, from about 25 to about 90 mol %, from about 30 to about85 mol %, from about 35 to about 80 mol %, from about 40 to about 75 mol%, or from about 50 to about 95 mol %; and (ii) from about 0.1 to about80 mol % of propylene, from about 5 mol % to about 70 mol %, from about10 to about 65 mol %, from about 15 to about 55 mol %, from about 25 toabout 50 mol %, or from about 30 to about 80 mol %; wherein the VT-HOcopolymer has at least 40% allyl chain ends, at least 50% allyl chainends, at least 60% allyl chain ends, at least 70% allyl chain ends; orat least 80% allyl chain ends; and, optionally, an isobutyl chain end toallyl chain end ratio of less than 0.70:1, less than 0.65:1, less than0.60:1, less than 0.50:1, or less than 0.25:1, and further optionally,an allyl chain end to vinylidene group ratio of more than 2:1, more than2.5:1, more than 3:1, more than 5:1, or more than 10:1.

In other embodiments, the invention relates to the use of a compositioncomprising VT-HO copolymers having an Mn of 300 g/mol or more,preferably 300 to 60,000 g/mol (measured by ¹H NMR) and comprises: (i)from about 80 to about 99.9 mol % of at least one C₄ olefin, preferablyabout 85 to about 99.9 mol %, more preferably about 90 to about 99.9 mol%; and (ii) from about 0.1 to about 20 mol % of propylene, preferablyabout 0.1 to about 15 mol %, more preferably about 0.1 to about 10 mol%; wherein the higher olefin copolymer has at least 40% allyl chainends, preferably at least 50% allyl chain ends, preferably at least 60%allyl chain ends, preferably at least 70% allyl chain ends, orpreferably at least 80% allyl chain ends; in some embodiments, anisobutyl chain end to allyl chain end ratio of less than 0.70:1, lessthan 0.65:1, less than 0.60:1, less than 0.50:1, or less than 0.25:1;and, in further embodiments, an allyl chain end to vinylidene groupratio of more than 2:1, more than 2.5:1, more than 3:1, more than 5:1,or more than 10:1.

In some embodiments, the composition is a lubricant blend.

In some embodiments, the invention relates to the use of the compositionas a lubricant blend.

Processes for Making Vinyl Terminated-Higher Olefin Copolymers

This invention also relates to relates to a process for making higherolefin copolymers, wherein the process comprises contacting, at atemperature of from 0 to 250° C., (preferably 35 to 150° C., preferablyfrom 40 to 120° C., preferably from 45 to 80° C.): (i) from about 20 toabout 99.9 mol % of at least one C₅ to C₄₀ higher olefin (preferablyfrom about 25 to about 90 mol %, from about 30 to about 85 mol %, fromabout 35 to about 80 mol %, from about 40 to about 75 mol %, or fromabout 50 to about 95 mol %); and (ii) from about 0.1 to about 80 mol %of propylene (preferably from about 5 mol % to about 70 mol %, fromabout 10 to about 65 mol %, from about 15 to about 55 mol %, from about25 to about 50 mol %, or from about 30 to about 80 mol %); wherein thecontacting occurs in the presence of a catalyst system comprising anactivator and at least one metallocene compound represented by at leastone of the formulae:

where M is hafnium or zirconium; each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system); each Q is,independently carbon or a heteroatom; each R¹ is, independently, a C₁ toC₈ alkyl group, R¹ may the same or different as R²; each R² is,independently, a C₁ to C₈ alkyl group; each R³ is, independently,hydrogen, or a substituted or unsubstituted hydrocarbyl group havingfrom 1 to 8 carbon atoms, provided however that at least three R³ groupsare not hydrogen; each R⁴ is, independently, hydrogen or a substitutedor unsubstituted hydrocarbyl group, a heteroatom or heteroatomcontaining group; R⁵ is hydrogen or a C₁ to C₈ alkyl group; R⁶ ishydrogen or a C₁ to C₈ alkyl group; each R⁷ is, independently, hydrogenor a C₁ to C₈ alkyl group, provided however that at least seven R⁷groups are not hydrogen; R₂ ^(a)T is a bridging group where T is a group14 element (preferably C, Si, or Ge, preferably Si) and each R^(a) is,independently, hydrogen, halogen or a C₁ to C₂₀ hydrocarbyl, and twoR^(a) can form a cyclic structure including aromatic, partiallysaturated, or saturated cyclic or fused ring system; and furtherprovided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated;

where M is hafnium or zirconium; each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system); each R⁸ is,independently, a C₁ to C₁₀ alkyl group; each R⁹ is, independently, a C₁to C₁₀ alkyl group; each R¹⁰ is hydrogen; each R¹¹, R¹², and R¹³, is,independently, hydrogen or a substituted or unsubstituted hydrocarbylgroup, a heteroatom or heteroatom containing group; T is a bridginggroup (such as R₂ ^(a)T as described above); and further provided thatany of adjacent R¹¹, R¹², and R¹³ groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated;

wherein M is hafnium or zirconium; each X is, independently, selectedfrom the group consisting of hydrocarbyl radicals having from 1 to 20carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halogens, dienes, amines, phosphines, ethers, or a combination thereof;each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group; and eachR¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ are,independently, hydrogen, or a substituted or unsubstituted hydrocarbylgroup having from 1 to 8 carbon atoms.

This invention also relates to a process for making higher olefincopolymers, wherein the process comprises contacting, underpolymerization conditions: (i) from about 80 to about 99.9 mol % of atleast one C₄ olefin, preferably about 85 to about 99.9 mol %, morepreferably about 90 to about 99.9 mol %; and (ii) from about 0.1 toabout 20 mol % of propylene, preferably about 0.1 to 15 about mol %,more preferably about 0.1 to about 10 mol %; wherein the contactingoccurs in the presence of a catalyst system comprising an activator andat least one metallocene compound represented by at least one of theformulae:

where M is hafnium or zirconium; each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system); each Q is,independently carbon or a heteroatom; each R¹ is, independently, a C₁ toC₈ alkyl group, R¹ may the same or different as R²; each R² is,independently, a C₁ to C₈ alkyl group; each R³ is, independently,hydrogen or a substituted or unsubstituted hydrocarbyl group having from1 to 8 carbon atoms, provided however that at least three R³ groups arenot hydrogen; each R⁴ is, independently, hydrogen or a substituted orunsubstituted hydrocarbyl group, a heteroatom or heteroatom containinggroup; R⁵ is hydrogen or a C₁ to C₈ alkyl group; R⁶ is hydrogen or a C₁to C₈ alkyl group; each R⁷ is, independently, hydrogen, or a C₁ to C₈alkyl group, provided however that at least seven R⁷ groups are nothydrogen; R₂ ^(a)T is a bridging group where T is a group 14 element(preferably C, Si, or Ge, preferably Si) and each R^(a) is, isindependently, hydrogen, halogen or a C₁ to C₂₀ hydrocarbyl, and twoR^(a) can form a cyclic structure including aromatic, partiallysaturated or saturated cyclic or fused ring system; and further providedthat any two adjacent R groups may form a fused ring or multicenterfused ring system where the rings may be aromatic, partially saturatedor saturated;

where M is hafnium or zirconium; each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, (two X'smay form a part of a fused ring or a ring system); each R⁸ is,independently, a C₁ to C₁₀ alkyl group; each R⁹ is, independently, a C₁to C₁₀ alkyl group; each R¹⁰ is hydrogen; each R¹¹, R¹², and R¹³, is,independently, hydrogen or a substituted or unsubstituted hydrocarbylgroup, a heteroatom or heteroatom containing group; T is a bridginggroup (such as R₂ ^(a)T as described above); and further provided thatany of adjacent R¹¹, R¹², and R¹³ groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated;

wherein M is hafnium or zirconium; each X is, independently, selectedfrom the group consisting of hydrocarbyl radicals having from 1 to 20carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halogens, dienes, amines, phosphines, ethers, or a combination thereof;each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group; and eachR¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ are,independently, hydrogen, or a substituted or unsubstituted hydrocarbylgroup having from 1 to 8 carbon atoms.

Generally, to make the VT-HO copolymers described herein, propylene andhigher olefin monomers (such as hexene or octene) may be copolymerizedby contacting: (i) one or more higher olefin monomer(s); and (ii)propylene monomer; wherein the contacting occurs in the presence of acatalyst system (comprising one or more metallocene compounds, and oneor more activators, described below). Other additives may also be used,as desired, such as one or more scavengers, promoters, modifiers,reducing agents, oxidizing agents, hydrogen, aluminum alkyls, orsilanes. In a preferred embodiment, little or no scavenger is used inthe process to produce the VT-HO copolymers. Preferably, scavenger ispresent at zero mol %, alternately, the scavenger is present at a molarratio of scavenger metal to transition metal of less than 100:1,preferably less than 50:1, preferably less than 15:1, preferably lessthan 10:1.

Higher olefin monomers useful herein are C₄ to C₄₀ olefins, preferablyC₅ to C₃₀ olefins, preferably C₆ to C₂₀ olefins, or preferably C₈ to C₁₂olefins. Where butene is the comonomer, the butene source may be a mixedbutene stream comprising various isomers of butene. The 1-butenemonomers are expected to be preferentially consumed by thepolymerization process.

The higher olefin monomers may be linear or cyclic. The higher olefincyclic olefins may be strained or unstrained, monocyclic or polycyclic,and may optionally include hetero atoms and/or one or more functionalgroups. Exemplary higher olefin monomers include butene, pentene,hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene,cyclopentene, cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene,substituted derivatives thereof, and isomers thereof, preferably hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, cyclopentene,norbornene, and their respective homologs and derivatives.

In some embodiments, where butene is the comonomer, the butene sourcemay be a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example, C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

Processes of this invention can be carried out in any manner known inthe art. Any suspension, homogeneous bulk, solution, slurry, or gasphase polymerization process known in the art can be used. Suchprocesses can be run in a batch, semi-batch, or continuous mode.Homogeneous polymerization processes and slurry are preferred. (Ahomogeneous polymerization process is defined to be a process where atleast 90 wt % of the product is soluble in the reaction media.) A bulkhomogeneous process is particularly preferred. (A bulk process isdefined to be a process where monomer concentration in all feeds to thereactor is 70 vol % or more.) Alternately, no solvent or diluent ispresent or added in the reaction medium, (except for the small amountsused as the carrier for the catalyst system or other additives, oramounts typically found with the monomer; e.g. propane in propylene).

In another embodiment, the process is a slurry process. As used hereinthe term “slurry polymerization process” means a polymerization processwhere a supported catalyst is employed and monomers are polymerized onthe supported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof such as can be foundcommercially (Isopar™); perhalogenated hydrocarbons such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof. In a preferred embodiment,aliphatic hydrocarbon solvents are used as the solvent, such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic, preferably aromatics are present in the solventat less than 1 wt %, preferably at 0.5 wt %, preferably at 0 wt % basedupon the weight of the solvents.

In a preferred embodiment, the feed concentration for the polymerizationis 60 vol % solvent or less, preferably 40 vol % or less, or preferably20 vol % or less, preferably 0 vol % based on the total volume of thefeedstream. Preferably the polymerization is run in a bulk process.

In some embodiments, the productivity is 4,500 g/mmol/hour or more,preferably 5,000 g/mmol/hour or more, preferably 10,000 g/mmol/hr ormore, preferably 50,000 g/mmol/hr or more. In other embodiments, theproductivity is at least 80,000 g/mmol/hr, preferably at least 150,000g/mmol/hr, preferably at least 200,000 g/mmol/hr, preferably at least250,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr. In analternate embodiment, the activity of the catalyst is at least 50g/mmol/hour, preferably 500 or more g/mmol/hour, preferably 5,000 ormore g/mmol/hr, preferably 50,000 or more g/mmol/hr. In an alternateembodiment, the conversion of olefin monomer is at least 10%, based uponpolymer yield and the weight of the monomer entering the reaction zone,preferably 20% or more, preferably 30% or more, preferably 50% or more,preferably 80% or more.

Preferred polymerizations can be run at any temperature and/or pressuresuitable to obtain the desired VT-HO copolymers. Typical temperaturesand/or pressures, such as at a temperature in the range of from about 0°C. to 250° C. (preferably 35° C. to 150° C., from 40° C. to 120° C.,from 45° C. to 80° C.); and at a pressure in the range of from about0.35 to 10 MPa (preferably from 0.45 to 6 MPa or from 0.5 to 4 MPa).

In a typical polymerization, the run time of the reaction is up to 300minutes, preferably in the range of from about 5 to 250 minutes, orpreferably from about 10 to 120 minutes.

In a preferred embodiment hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa),preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1to 10 psig (0.7 to 70 kPa). It has been found that in the presentsystems, hydrogen can be used to provide increased activity withoutsignificantly impairing the catalyst's ability to produce allylic chainends. Preferably, the catalyst activity (calculated as g/mmolcatalyst/hr) is at least 20% higher than the same reaction withouthydrogen present, preferably at least 50% higher, preferably at least100% higher.

In a preferred embodiment, little or no alumoxane is used in the processto produce the vinyl terminated polymers. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to transition metal less than 500:1, preferably lessthan 300:1, preferably less than 100:1, preferably less than 1:1.

In an alternate embodiment, if an alumoxane is used to produce the vinylterminated polymers then, the alumoxane has been treated to remove freealkyl aluminum compounds, particularly trimethyl aluminum.

Further, in a preferred embodiment, the activator used herein to producethe vinyl terminated polymer is a bulky activator as defined herein andis discrete.

In a preferred embodiment, little or no scavenger is used in the processto produce the vinyl terminated polymers. Preferably, scavenger (such astri alkyl aluminum) is present at zero mol %, alternately the scavengeris present at a molar ratio of scavenger metal to transition metal ofless than 100:1, preferably less than 50:1, preferably less than 15:1,preferably less than 10:1.

In a preferred embodiment, the polymerization: 1) is conducted attemperatures of 0 to 300° C. (preferably 25 to 150° C., preferably 40 to120° C., preferably 45 to 80° C.), and 2) is conducted at a pressure ofatmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferablyfrom 0.45 to 6 MPa, preferably from 0.5 to 4 MPa), and 3) is conductedin an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; preferably where aromatics are present in the solvent at lessthan 1 wt %, preferably at less than 0.5 wt %, preferably at 0 wt %based upon the weight of the solvents); and 4) wherein the catalystsystem used in the polymerization comprises less than 0.5 mol %,preferably 0 mol % alumoxane, alternately the alumoxane is present at amolar ratio of aluminum to transition metal less than 500:1, preferablyless than 300:1, preferably less than 100:1, preferably less than 1:1;and 5) the polymerization occurs in one reaction zone; and 6) theproductivity of the catalyst compound is at least 80,000 g/mmol/hr(preferably at least 150,000 g/mmol/hr, preferably at least 200,000g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably at least300,000 g/mmol/hr); and 7) optionally scavengers (such as trialkylaluminum compounds) are absent (e.g. present at zero mol %, alternatelythe scavenger is present at a molar ratio of scavenger metal totransition metal of less than 100:1, preferably less than 50:1,preferably less than 15:1, preferably less than 10:1); and 8) optionallyhydrogen is present in the polymerization reactor at a partial pressureof 0.001 to 50 psig (0.007 to 345 kPa) (preferably from 0.01 to 25 psig(0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)). Inpreferred embodiment, the catalyst system used in the polymerizationcomprises no more than one catalyst compound. A “reaction zone” alsoreferred to as a “polymerization zone” is a vessel where polymerizationtakes place, for example a batch reactor. When multiple reactors areused in either series or parallel configuration, each reactor isconsidered as a separate polymerization zone. For a multi-stagepolymerization in both a batch reactor and a continuous reactor, eachpolymerization stage is considered as a separate polymerization zone. Ina preferred embodiment, the polymerization occurs in one reaction zone.Room temperature is 23° C. unless otherwise noted.

Catalyst Systems

In embodiments herein, the invention relates to a process for makinghigher olefin copolymers, wherein the process comprises contacting thepropylene and higher olefin monomers in the presence of a catalystsystem comprising an activator and at least one metallocene compound, asshown below.

In the description herein, the metallocene catalyst may be described asa catalyst precursor, a pre-catalyst compound, or a transition metalcompound, and these terms are used interchangeably. A polymerizationcatalyst system is a catalyst system that can polymerize monomers topolymer. A “catalyst system” is combination of at least one catalystcompound, at least one activator, an optional co-activator, and anoptional support material. An “anionic ligand” is a negatively chargedligand which donates one or more pairs of electrons to a metal ion. A“neutral donor ligand” is a neutrally charged ligand which donates oneor more pairs of electrons to a metal ion.

For the purposes of this invention and the claims thereto, when catalystsystems are described as comprising neutral stable forms of thecomponents, it is well understood by one of ordinary skill in the art,that the ionic form of the component is the form that reacts with themonomers to produce polymers.

A metallocene catalyst is defined as an organometallic compound with atleast one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety) and more frequently two π-boundcyclopentadienyl-moieties or substituted moieties. This includes otherπ-bound moieties such as indenyls or fluorenyls or derivatives thereof.

The metallocene, activator, optional co-activator, and optional supportcomponents of the catalyst system are discussed below.

(a) Metallocene Component

The term “substituted” means that a hydrogen group has been replacedwith a hydrocarbyl group, a heteroatom, or a heteroatom containinggroup. For example, methyl cyclopentadiene (Cp) is a Cp groupsubstituted with a methyl group, ethyl alcohol is an ethyl groupsubstituted with an —OH group, and a “substituted hydrocarbyl” is aradical made of carbon and hydrogen where at least one hydrogen isreplaced by a heteroatom.

For purposes of this invention and claims thereto, “alkoxides” includethose where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl groupmay be straight chain, branched, or cyclic. The alkyl group may besaturated or unsaturated. In some embodiments, the alkyl group maycomprise at least one aromatic group.

The metallocene component of the catalyst system is represented by atleast one of the formulae I, II, III, IV, V, or VI.

(i) Formulae I, II, III, and IV

In some embodiments, the metallocene compound is represented by at leastone of Formulae I, II, III, and IV.

where M is hafnium or zirconium;

-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof; preferably methyl,    ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide,    (alternately two X's may form a part of a fused ring or a ring    system);-   each Q is, independently carbon or a heteroatom, preferably C, N, P,    S (preferably at least one Q is a heteroatom, alternately at least    two Q's are the same or different heteroatoms, alternately at least    three Q's are the same or different heteroatoms, alternately at    least four Q's are the same or different heteroatoms);-   each R¹ is, independently, hydrogen or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹ may the same or    different as R²;-   each R² is, independently, hydrogen or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided that at    least one of R¹ or R² is not hydrogen, preferably both of R¹ and R²    are not hydrogen, preferably R¹ and/or R² are not branched;-   each R³ is, independently, hydrogen, or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    preferably 1 to 6 carbon atoms, preferably a substituted or    unsubstituted C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl, octyl, provided however that    at least three R³ groups are not hydrogen (alternately four R³    groups are not hydrogen, alternately five R³ groups are not    hydrogen);-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group, preferably a substituted or unsubstituted    hydrocarbyl group having from 1 to 20 carbon atoms, preferably 1 to    8 carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl),    phenyl, silyl, substituted silyl, (such as CH₂SiR′, where R′ is a C₁    to C₁₂ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl);-   R⁵ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group, preferably a C₁ to C₈    linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, heptyl or octyl;-   each R⁷ is, independently, hydrogen or a C₁ to C₈ alkyl group,    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, provided however that    at least seven R⁷ groups are not hydrogen, alternately at least    eight R⁷ groups are not hydrogen, alternately all R⁷ groups are not    hydrogen, (preferably the R⁷ groups at the 3 and 4 positions on each    Cp ring of Formula IV are not hydrogen);-   R₂ ^(a)T is a bridging group, preferably T is C, Si or Ge,    preferably Si;-   each R^(a), is independently, hydrogen, halogen or a C₁ to C₂₀    hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) can    form a cyclic structure including aromatic, partially saturated, or    saturated cyclic or fused ring system; and further provided that any    two adjacent R groups may form a fused ring or multicenter fused    ring system where the rings may be aromatic, partially saturated or    saturated.

In an alternate embodiment, at least one R⁴ group is not hydrogen,alternately at least two R⁴ groups are not hydrogen, alternately atleast three R⁴ groups are not hydrogen, alternately at least four R⁴groups are not hydrogen, alternately all R⁴ groups are not hydrogen.

In some embodiments, the bridging group R₂ ^(a)T includes bridginggroups containing at least one Group 13 to 16 atom, often referred to asa divalent moiety, such as, but not limited to, at least one of acarbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tinatom, or a combination thereof. Preferably, bridging group T contains acarbon, silicon or germanium atom, most preferably, T contains at leastone silicon atom or at least one carbon atom. The bridging group T mayalso contain substituent groups R* as defined below including halogensand iron.

Non-limiting examples of substituent groups R* include one or more fromthe group selected from hydrogen, or linear, or branched alkyl radicals,alkenyl radicals, alkenyl radicals, cycloalkyl radicals, aryl radicals,acyl radicals, aryl radicals, alkoxy radicals, aryloxy radicals,alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,arylamino radicals or combination thereof. In a preferred embodiment,substituent groups R* have up to 50 non-hydrogen atoms, preferably from1 to 30 carbon, that may also be substituted with halogens orheteroatoms or the like. Non-limiting examples of alkyl substituents R*include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl,cyclohexyl, benzyl or phenyl groups and the like, including all theirisomers, for example tertiary butyl, isopropyl, and the like. Otherhydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl,iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substitutedorganometalloid radicals including trimethylsilyl, trimethylgermyl,methyldiethylsilyl and the like; and halocarbyl-substitutedorganometalloid radicals including tris(trifluoromethyl)silyl,methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like;and disubstituted boron radicals including dimethylboron for example;and disubstituted pnictogen radicals including dimethylamine,dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogenradicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide andethylsulfide. Non-hydrogen substituents R* include the atoms carbon,silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur,germanium and the like, including olefins, such as, but not limited to,olefinically unsaturated substituents including vinyl-terminatedligands, for example, but-3-enyl, prop-2-enyl, hex-5-enyl and the like.Also, in some embodiments, at least two R* groups, preferably twoadjacent R groups, are joined to form a ring structure having from 3 to30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon,germanium, aluminum, boron or a combination thereof. In otherembodiments, R* may also be a diradical bonded to L at one end andforming a carbon sigma bond to the metal M. Particularly preferred, R*substituent groups include a C₁ to C₃₀ hydrocarbyl, a heteroatom orheteroatom containing group (preferably methyl, ethyl, propyl (includingisopropyl, sec-propyl), butyl (including t-butyl and sec-butyl),neopentyl, cyclopentyl, hexyl, octyl, nonyl, decyl, phenyl, substitutedphenyl, benzyl (including substituted benzyl), cyclohexyl, cyclododecyl,norbornyl, and all isomers thereof.

Examples of bridging group R₂ ^(a)T in formula III or T in formula Vuseful herein may be represented by R′₂C, R′₂Si, R′₂Ge, R′₂CCR′₂,R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂,R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂, R₂CSiR′₂CR′₂,R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂, R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂,R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂,R′₂C—O—CR′₂, R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C-β-CR′═CR′,R′₂C—S—CR′₂, R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′,R′₂C—Se—CR′₂, R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR₂CR′₂, R′₂C—Se—CR′═CR′,R′₂C—N═CR′, R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′,R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—CR′₂ where R′ ishydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbylsubstituent and optionally two or more adjacent R′ may join to form asubstituted or unsubstituted, saturated, partially unsaturated oraromatic, cyclic or polycyclic substituent. Preferably, the bridginggroup comprises carbon or silica, such as dialkylsilyl, preferably thebridging group is selected from CH₂, CH₂CH₂, C(CH₃)₂, SiMe₂, SiPh₂,SiMePh, silylcyclobutyl (Si(CH₂)₃, (Ph)₂C, (p-(Et)₃SiPh)₂C andsilylcyclopentyl (Si(CH₂)₄).

Catalyst compounds that are particularly useful in this inventioninclude one or more of:

-   (1,3-dimethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3,4,7-tetramethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3-dimethylindenyl)(tetramethylcyclopentadienyl)hafniumdimethyl,-   (1,3-diethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3-dipropylindenyl)(pentamethylcyclopentadienyl)hathiumdimethyl,-   (1-methyl,3-propyllindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3-dimethylindenyl)(tetramethylpropylcyclopentadienyl)hafniumdimethyl,-   (1,2,3-trimethylindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (1,3-dimethylbenzindenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (2,7-bis    t-butylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   (9-methylfluorenyl)(pentamethylcyclopentadienyl)hathiumdimethyl,-   (2,7,9-trimethylfluorenyl)(pentamethylcyclopentadienyl)hafniumdimethyl,-   dihydrosilylbis(tetramethylcyclopentadienyl)hafniumdimethyl,-   dihydrosilylbis(tetramethylcyclopentadienyl)hafniumdimethyl,-   dimethylsilyl(tetramethylcyclopentadienyl)(3-propyltrimethylcyclopentadienyl)hafniumdimethyl,    and-   dicyclopropylsilylbis(tetramethylcyclopentadienyl)hafniumdimethyl.

In an alternate embodiment, the “dimethyl” after the transition metal inthe list of catalyst compounds above is replaced with a dihalide (suchas dichloride or difluoride) or a bisphenoxide, particularly for usewith an alumoxane activator.

(ii) Formula V

In some embodiments, the metallocene may be represented by Formula V,below.

where M is hafnium or zirconium, preferably hafnium;

-   each X is, independently, selected from the group consisting of a    substituted or unsubstituted hydrocarbyl radicals having from 1 to    20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,    halides, dienes, amines, phosphines, ethers, and a combination    thereof (two X's may form a part of a fused ring or a ring system);    preferably each X is independently selected from halides and C₁ to    C₆ hydrocarbyl groups, preferably each X is methyl, ethyl, propyl,    butyl, phenyl, benzyl, chloride, bromide, or iodide;-   each R⁸ is, independently, a substituted or unsubstituted C₁ to C₁₀    alkyl group; preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, nonyl, decyl, or isomers thereof; preferably methyl,    n-propyl, or n-butyl; or preferably methyl;-   each R⁹ is, independently, a substituted or unsubstituted C₁ to C₁₀    alkyl group; preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, nonyl, decyl, or isomers thereof; preferably methyl,    n-propyl, or butyl; or preferably n-propyl;-   each R¹⁰ is hydrogen;-   each R¹¹, R¹², and R¹³, is, independently, hydrogen or a substituted    or unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group; preferably each R¹¹, R¹², and R¹³, is hydrogen;-   T is a bridging group represented by the formula R₂ ^(a)J where J is    C, Si or Ge, preferably Si;-   each R^(a) is, independently, hydrogen, halogen or a C₁ to C₂₀    hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,    heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R^(a) can    form a cyclic structure including aromatic, partially saturated or    saturated cyclic or fused ring system;-   further provided that any two adjacent R groups may form a fused    ring or multicenter fused ring system where the rings may be    aromatic, partially saturated or saturated. T may also be a bridging    group as defined above for R₂ ^(a)T; and-   further provided that any of adjacent R¹¹, R¹², and R¹³ groups may    form a fused ring or multicenter fused ring system where the rings    may be aromatic, partially saturated or saturated.

Metallocene compounds that are particularly useful in this inventioninclude one or more of:

-   rac-dimethylsilyl bis(2-methyl,3-propylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-ethyl,3-propylindenyl)hafniumdimethyl;-   rac-dimethylsilyl bis(2-ethyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-ethylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-ethylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-isopropylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-isopropylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-butyllindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-butylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-ethyl,3-propylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-ethyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-ethylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-ethylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl    bis(2-methyl,3-isopropylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl    bis(2-methyl,3-isopropylindenyl)zirconiumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-butyllindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2-methyl,3-propylindenyl)zirconiumdimethyl,-   rac-dimethylsilyl bis(2-propyl,3-methylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-propyl,3-ethylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-propyl,3-butylindenyl)hafniumdimethyl,-   rac-dimethylsilyl bis(2-methyl,3-butylindenyl)hafniumdimethyl,-   rac-dimethylgermanyl bis(2,3-dimethylindenyl)hafnium dimethyl,-   rac-dimethylsilyl bis(2,3-dimethylindenyl)hafnium dimethyl, and-   rac-dimethylsilyl bis(2,3-diethylindenyl)hafnium dimethyl.

In an alternate embodiment, the “dimethyl” after the transition metal inthe list of catalyst compounds above is replaced with a dihalide (suchas dichloride or difluoride) or a bisphenoxide, particularly for usewith an alumoxane activator.

In particular embodiments, the metallocene compound is rac-dimethylsilylbis(2-methyl,3-propylindenyl)hafniumdimethyl (V-I), rac-dimethylsilylbis(2-methyl,3-propylindenyl)zirconiumdimethyl (V-II), represented bythe formulae below:

In some embodiments, the metallocene may be represented by Formula VI,below.

-   wherein M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof;-   each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group;    preferably a C₁ to C₈ linear alkyl group, preferably methyl ethyl,    propyl, butyl, pentyl, hexyl, heptyl or octyl, R¹⁵ may be the same    or different as R¹⁷, and preferably are both methyl; and-   each R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸    are, independently, hydrogen or a substituted or unsubstituted    hydrocarbyl group having from 1 to 8 carbon atoms; preferably 1 to 6    carbon atoms, preferably a substituted or unsubstituted C₁ to C₈    linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl,    hexyl, heptyl, octyl, provided however that at least three of    R²⁴-R²⁸ groups are not hydrogen (alternately four of R²⁴-R²⁸ groups    are not hydrogen, alternately five of R²⁴-R²⁸ groups are not    hydrogen); 1) preferably all five groups of R²⁴-R²⁸ are methyl,    or 2) four of the R²⁴-R²⁸ groups are not hydrogen and at least one    of the R²⁴-R²⁸ groups is a C₂ to C₈ substituted or unsubstituted    hydrocarbyl (preferably at least two, three, four or five of R²⁴-R²⁸    groups are a C₂ to C₈ substituted or unsubstituted hydrocarbyl).

In one embodiment, R¹⁵ and R¹⁷ are methyl groups, R¹⁶ is a hydrogen,R¹⁸-R²³ are all hydrogens, R²⁴-R²⁸ are all methyl groups, and each X isa methyl group.

Catalyst compounds that are particularly useful in this inventioninclude (CpMe₅)(1,3-Me₂-benz[e]indenyl)HfMe₂,(CpMe₅)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-n-propyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-ethyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₅)(1-methyl,3-ethylbenz[e]indenyl)HfMe₂,(CpMe₄n-propyl)(1,3-Me₂-benz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl) (1-n-propyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl) (1-ethyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄-n-propyl)(1-methyl,3-ethylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1,3-Me₂-benz[e]indenyl)HfMe₂, (CpMe₄n-butyl)(1-methyl-3-n-propylbenz[e]indenyl)HfMe₂, (CpMe₄n-butyl)(1-n-propyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl-3-n-butylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-n-butyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-ethyl,3-methylbenz[e]indenyl)HfMe₂,(CpMe₄n-butyl)(1-methyl,3-ethylbenz[e]indenyl)HfMe₂, and the zirconiumanalogs thereof.

In an alternate embodiment, the “dimethyl” (Me₂) after the transitionmetal in the list of catalyst compounds above is replaced with adihalide (such as dichloride or difluoride) or a bisphenoxide,particularly for use with an alumoxane activator.

(b) Activator Component of Catalyst System

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract one reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxideor amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. Another alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator at a 5000-fold molarexcess Al/M over the catalyst precursor (per metal catalytic site). Theminimum activator-to-catalyst-precursor is a 1:1 molar ratio. Alternatepreferred ranges include up to 500:1, alternately up to 200:1,alternately up to 100:1, or alternately from 1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in theprocess to produce the VT-HO copolymers. Preferably, alumoxane ispresent at zero mol %, alternately the alumoxane is present at a molarratio of aluminum to transition metal less than 500:1, preferably lessthan 300:1, preferably less than 100:1, preferably less than 1:1. In analternate embodiment, if an alumoxane is used to produce the VT-HOcopolymers then, the alumoxane has been treated to remove free alkylaluminum compounds, particularly trimethyl aluminum. Further, in apreferred embodiment, the activator used herein to produce the VT-HOcopolymers is bulky as defined herein and is discrete.

Aluminum alkyl or organoaluminum compounds which may be utilized asco-activators (or scavengers) include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, and the like.

Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl) borate, a tris perfluorophenyl boronmetalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators. Preferredactivators are the ionic activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy, andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,alkenyl compounds, and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 3 to20 carbon atoms (including substituted aryls). More preferably, thethree groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP 0 570982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A;EP 0 277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741;5,206,197; 5,241,025; 5,384,299; 5,502,124; and U.S. patent applicationSer. No. 08/285,380, filed Aug. 3, 1994; all of which are herein fullyincorporated by reference.

Ionic catalysts can be preparedly reacting a transition metal compoundwith some neutral Lewis acids, such as B(C₆F₆)₃, which upon reactionwith the hydrolyzable ligand (X) of the transition metal compound formsan anion, such as ([B(C₆F₅)₃(X)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components which areionic compounds or compositions.

Compounds useful as an activator component in the preparation of theionic catalyst systems used in the process of this invention comprise acation, which is preferably a Bronsted acid capable of donating aproton, and a compatible non-coordinating anion which anion isrelatively large (bulky), capable of stabilizing the active catalystspecies (the Group 4 cation) which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, amines and the like. Two classes ofcompatible non-coordinating anions have been disclosed in Europeanpublications EP 0 277 003 A and EP 0 277 004 A, published 1988: 1)anionic coordination complexes comprising a plurality of lipophilicradicals covalently coordinated to and shielding a centralcharge-bearing metal or metalloid core, and 2) anions comprising aplurality of boron atoms such as carboranes, metallacarboranes andboranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L-H)_(d) ⁺(A^(d−))  (14)wherein L is a neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronstedacid; A^(d−) is a non-coordinating anion having the charge d−; and d is1 2, or 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotonated Lewis bases capable of protonating a moiety, such as an alkylor aryl, from the bulky ligand metallocene containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 2, 3, 4, 5, or 6;n−k=d; M is an element selected from Group 13 of the Periodic Table ofthe Elements, preferably boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having upto 20 carbon atoms with the proviso that in not more than 1 occurrenceis Q a halide. Preferably, each Q is a fluorinated hydrocarbyl grouphaving 1 to 20 carbon atoms, more preferably each Q is a fluorinatedaryl group, and most preferably each Q is a pentafluoryl aryl group.Examples of suitable A^(d−) also include diboron compounds as disclosedin U.S. Pat. No. 5,447,895, which is fully incorporated herein byreference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the catalystsystem of the processes of this invention are tri-substituted ammoniumsalts such as: trimethylammonium tetraphenylborate, triethylammoniumtetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, anddialkyl ammonium salts such as: di-(1-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and additional tri-substitutedphosphonium salts such as tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Most preferably, the ionic stoichiometric activator (L-H)_(d) ⁺ (A^(d−))is, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetrakis(perfluorophenyl)borate.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a bulky ligandmetallocene catalyst cation and their non-coordinating anion are alsocontemplated, and are described in European publications EP 0 426 637 A,EP 0 573 403 A, and U.S. Pat. No. 5,387,568, which are all hereinincorporated by reference.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-cordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral fourcoordinate metallocene compound and a neutral by-product from the anion.Non-coordinating anions useful in accordance with this invention arethose that are compatible, stabilize the metallocene cation in the senseof balancing its ionic charge at +1, yet retain sufficient lability topermit displacement by an ethylenically or acetylenically unsaturatedmonomer during polymerization. In addition to these activator compoundsor co-catalysts, scavengers are used such as tri-isobutyl aluminum ortri-octyl aluminum.

Inventive processes also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the invention compounds. For example,tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbylor hydride ligand to yield an invention cationic metal complex andstabilizing noncoordinating anion, see European publications EP 0 427697 A and EP 0 520 732 A for illustrations of analogous Group-4metallocene compounds. Also, see the methods and compounds of EP 0 495375 A. For formation of zwitterionic complexes using analogous Group 4compounds, see U.S. Pat. Nos. 5,624,878; 5,486,632; and 5,527,929.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(OX^(e+))_(d)(A^(d−))_(e)  (16)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2 or 3; and A^(d−) is a non-coordinating anion having the charged−; and d is 1, 2 or 3. Examples of cationic oxidizing agents include:ferrocenium, hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺².Preferred embodiments of A^(d−) are those anions previously defined withrespect to the Bronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

The typical NCA (or non-alumoxane activator) activator-to-catalyst ratiois a 1:1 molar ratio. Alternate preferred ranges include from 0.1:1 to100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1alternately from 1:1 to 1000:1. A particularly useful range is from0.5:1 to 10:1, preferably 1:1 to 5:1.

Bulky Activators

“Bulky activator” as used herein refers to anionic activatorsrepresented by the formula:

where:

-   each R₁ is, independently, a halide, preferably a fluoride;-   each R₂ is, independently, a halide, a C₆ to C₂₀ substituted    aromatic hydrocarbyl group or a siloxy group of the formula    —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or    hydrocarbylsilyl group (preferably R₂ is a fluoride or a    perfluorinated phenyl group);-   each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl    group or a siloxy group of the formula —O—Si—R_(a), where R_(a) is a    C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a    fluoride or a C₆ perfluorinated aromatic hydrocarbyl group); wherein    R₂ and R₃ can form one or more saturated or unsaturated, substituted    or unsubstituted rings (preferably R₂ and R₃ form a perfluorinated    phenyl ring);-   L is a neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or    3;-   wherein the anion has a molecular weight of greater than 1020 g/mol;    and-   wherein at least three of the substituents on the B atom each have a    molecular volume of greater than 250 cubic Å, alternately greater    than 300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3V_(S), where V_(S) is the scaledvolume. V_(S) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Molecular MV Formula of Per Total Structure of boron each subst. MVActivator substituents substituent V_(s) (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoro- naphthyl)borate

C₁₀F₇ 34 261 1044 Dimethylanilinium tetrakis(perfluoro- biphenyl)borate

C₁₂F₉ 42 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

Exemplary bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the types disclosed in U.S.Pat. No. 7,297,653.

Activator Combinations

It is within the scope of this invention that catalyst compounds can becombined with one or more activators or activation methods describedabove. For example, a combination of activators have been described inU.S. Pat. Nos. 5,153,157; 5,453,410; European publication EP 0 573 120B1; PCT publications WO 94/07928; and WO 95/14044. These documents alldiscuss the use of an alumoxane in combination with an ionizingactivator.

(iii) Optional Co-Activators and Scavengers

In addition to these activator compounds, scavengers or co-activatorsmay be used. Aluminum alkyl or organoaluminum compounds which may beutilized as co-activators (or scavengers) include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, and tri-n-octylaluminum.

(iv) Optional Support Materials

In embodiments herein, the catalyst system may comprise an inert supportmaterial. Preferably the supported material is a porous supportmaterial, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in metallocenecatalyst systems herein include Groups 2, 4, 13, and 14 metal oxidessuch as silica, alumina and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, for example, finely dividedfunctionalized polyolefins such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania and the like. Preferredsupport materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof,more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g, and average particle size of from about 10 to about 200 μm.Most preferably, the surface area of the support material is in therange is from about 100 to about 400 m²/g, pore volume from about 0.8 toabout 3.0 cc/g, and average particle size is from about 5 to about 100μm. The average pore size of the support material useful in theinvention is in the range of from 10 to 1000 Å, preferably 50 to about500 Å, and most preferably 75 to about 350 Å. In some embodiments, thesupport material is a high surface area, amorphous silica (surfacearea=300 m²/gm; pore volume of 1.65 cm³/gm), examples of which aremarketed under the tradenames of DAVISON 952 or DAVISON 955 by theDavison Chemical Division of W.R. Grace and Company. In otherembodiments DAVIDSON 948 is used.

The support material should be dry, that is, free of absorbed water.Drying of the support material can be effected by heating or calciningat about 100° C. to about 1000° C., preferably at least about 600° C.When the support material is silica, it is heated to at least 200° C.,preferably about 200° C. to about 850° C., and most preferably at about600° C.; and for a time of about 1 minute to about 100 hours, from about12 hours to about 72 hours, or from about 24 hours to about 60 hours.The calcined support material must have at least some reactive hydroxyl(OH) groups to produce the catalyst system of this invention. Thecalcined support material is then contacted with at least onepolymerization catalyst comprising at least one metallocene compound andan activator.

Methods of Making the Supported Catalyst Systems

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a metallocene compound and an activator.The slurry of the support material in the solvent is prepared byintroducing the support material into the solvent, and heating themixture to about 0° C. to about 70° C., preferably to about 25° C. toabout 60° C., preferably at room temperature. Contact times typicallyrange from about 0.5 hours to about 24 hours, from about 0.5 hours toabout 8 hours, or from about 0.5 hours to about 4 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator, and the metallocene compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

In embodiments herein, the support material is contacted with a solutionof a metallocene compound and an activator, such that the reactivegroups on the support material are titrated, to form a supportedpolymerization catalyst. The period of time for contact between themetallocene compound, the activator, and the support material is as longas is necessary to titrate the reactive groups on the support material.To “titrate” is meant to react with available reactive groups on thesurface of the support material, thereby reducing the surface hydroxylgroups by at least 80%, at least 90%, at least 95%, or at least 98%. Thesurface reactive group concentration may be determined based on thecalcining temperature and the type of support material used. The supportmaterial calcining temperature affects the number of surface reactivegroups on the support material available to react with the metallocenecompound and an activator: the higher the drying temperature, the lowerthe number of sites. For example, where the support material is silicawhich, prior to the use thereof in the first catalyst system synthesisstep, is dehydrated by fluidizing it with nitrogen and heating at about600° C. for about 16 hours, a surface hydroxyl group concentration ofabout 0.7 millimoles per gram (mmols/gm) is typically achieved. Thus,the exact molar ratio of the activator to the surface reactive groups onthe carrier will vary. Preferably, this is determined on a case-by-casebasis to assure that only so much of the activator is added to thesolution as will be deposited onto the support material without leavingexcess of the activator in the solution.

The amount of the activator which will be deposited onto the supportmaterial without leaving excess in the solution can be determined in anyconventional manner, e.g., by adding the activator to the slurry of thecarrier in the solvent, while stirring the slurry, until the activatoris detected as a solution in the solvent by any technique known in theart, such as by ¹H NMR. For example, for the silica support materialheated at about 600° C., the amount of the activator added to the slurryis such that the molar ratio of B to the hydroxyl groups (OH) on thesilica is about 0.5:1 to about 4:1, preferably about 0.8:1 to about 3:1,more preferably about 0.9:1 to about 2:1 and most preferably about 1:1.The amount of B on the silica may be determined by using ICPES(Inductively Coupled Plasma Emission Spectrometry), which is describedin J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in the Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644. In another embodiment, it is alsopossible to add such an amount of activator which is in excess of thatwhich will be deposited onto the support, and then remove, e.g., byfiltration and washing, any excess of the activator.

In another embodiment this invention relates to:

-   1. A higher olefin copolymer having an Mn of 300 g/mol or more    (measured by ¹H NMR), preferably 300 to 60,000 g/mol preferably 400    to 50,000 g/mol, preferably 500 to 35,000 g/mol, preferably 300 to    15,000 g/mol, preferably 400 to 12,000 g/mol, or preferably 750 to    10,000 g/mol, comprising:-   (i) from about 20 to about 99.9 mol % of at least one C₅ to C₄₀    higher olefin, from about 25 to about 90 mol %, from about 30 to    about 85 mol %, from about 35 to about 80 mol %, from about 40 to    about 75 mol %, or from about 50 to about 95 mol % of at least one    C₅ to C₄₀ higher olefin, preferably two or more C₅ to C₄₀ higher    olefins (preferably selected from pentene, hexene, heptene, octene,    nonene, decene, undecene, dodecene, norbornene, norbornadiene,    dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,    cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,    substituted derivatives thereof, and isomers thereof); and-   (ii) from about 0.1 to about 80 mol % of propylene, from about 5 mol    % to about 70 mol %, from about 10 to about 65 mol %, from about 15    to about 55 mol %, from about 25 to about 50 mol %, or from about 30    to about 80 mol %;-   wherein the higher olefin copolymer has at least 40% allyl chain    ends, at least 50% allyl chain ends, at least 60% allyl chain ends,    at least 70% allyl chain ends, or at least 80% allyl chain ends, at    least 90% allyl chain ends, at least 95% allyl chain ends;-   in some embodiments, an isobutyl chain end to allyl chain end ratio    of less than 0.70:1, less than 0.65:1, less than 0.60:1, less than    0.50:1, or less than 0.25:1, and-   in other embodiments, an allyl chain end to vinylidene group ratio    of more than 2:1, more than 2.5:1, more than 3:1, more than 5:1, or    more than 10:1.-   2. The higher olefin copolymer of paragraph 1, wherein the higher    olefin copolymer comprises at least 50 wt %, based upon the weight    of the copolymer composition, of olefins having at least 36 carbon    atoms, as measured by ¹H NMR, assuming one unsaturation per chain.-   3. The higher olefin copolymer of paragraphs 1 and 2, wherein the    higher olefin copolymer comprises less than 20 wt % dimer and    trimer, preferably less than 10 wt %, preferably less than 5 wt %,    or more preferably less than 2 wt %, based upon the weight of the    copolymer composition.-   4. The higher olefin copolymer of paragraphs 1 to 3, wherein the    higher olefin copolymer has a viscosity at 60° C. of greater than    1,000 cP, greater than 12,000 cP, or greater than 100,000 cP    (alternatively less than 200,000 cP, less than 150,000 cP, or less    than 100,000 cP).-   5. A higher olefin copolymer having an Mn of 300 g/mol or more    (measured by ¹H NMR), preferably 300 to 60,000 g/mol and    comprising: (i) from about 80 to about 99.9 mol % of at least one C₄    olefin, preferably about 85 to about 99.9 mol %, more preferably    about 90 to about 99.9 mol %; and (ii) from about 0.1 to about 20    mol % of propylene, preferably about 0.1 to about 15 mol %, more    preferably about 0.1 to about 10 mol %; wherein the higher olefin    copolymer has at least 40% allyl chain ends, preferably at least 50%    allyl chain ends, at least 60% allyl chain ends, at least 70% allyl    chain ends, or at least 80% allyl chain ends, at least 90% allyl    chain ends, at least 95% allyl chain ends; and-   in some embodiments, an isobutyl chain end to allyl chain end ratio    of less than 0.70:1, less than 0.65:1, less than 0.60:1, less than    0.50:1, or less than 0.25:1, and in further embodiments, an allyl    chain end to vinylidene group ratio of more than 2:1, more than    2.5:1, more than 3:1, more than 5:1, or more than 10:1.-   6. A process for making the higher olefin copolymers of paragraphs 1    to 4, wherein the process comprises contacting:-   (i) from about 20 to about 99.9 mol % of at least one C₅ to C₄₀    higher olefin, (preferably from about 25 to about 90 mol %, from    about 30 to about 85 mol %, from about 35 to about 80 mol %, from    about 40 to about 75 mol %, or from about 50 to about 95 mol %);    preferably two or more C₅ to C₄₀ higher olefins (preferably selected    from butene, pentene, hexene, heptene, octene, nonene, decene,    undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene,    cyclopentene, cycloheptene, cyclooctene, cyclooctadiene,    cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted    derivatives thereof, and isomers thereof); and-   (ii) from about 0.1 to about 80 mol % of propylene, (preferably from    about 5 mol % to about 70 mol %, from about 10 to about 65 mol %,    from about 15 to about 55 mol %, from about 25 to about 50 mol %, or    from about 30 to about 80 mol %); and-   (iii) optionally, ethylene;-   wherein the contacting occurs in the presence of a catalyst system    comprising an activator and at least one metallocene compound    represented by at least one of the formulae:

where:

-   M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, and a combination thereof, (two X's may form a    part of a fused ring or a ring system);-   each Q is, independently carbon or a heteroatom;-   each R¹ is, independently, a C₁ to C₈ alkyl group, R¹ may the same    or different as R²;-   each R² is, independently, a C₁ to C₈ alkyl group;-   each R³ is, independently, hydrogen, or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    provided however that at least three R³ groups are not hydrogen;-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group;-   R⁵ is hydrogen or a C₁ to C₈ alkyl group;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group;-   each R⁷ is, independently, hydrogen or a C₁ to C₈ alkyl group,    provided however that at least seven R⁷ groups are not hydrogen;-   R₂ ^(a)T is a bridging group, where T is a group 14 element    (preferably C, Si, or Ge);-   each R^(a) is, independently, hydrogen, halogen or a C₁ to C₂₀    hydrocarbyl; and-   two R^(a) can form a cyclic structure including aromatic, partially    saturated, or saturated cyclic or fused ring system; and further    provided that any two adjacent R groups may form a fused ring or    multicenter fused ring system where the rings may be aromatic,    partially saturated or saturated;

where:

-   M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halides, dienes, amines,    phosphines, ethers, and a combination thereof, (two X's may form a    part of a fused ring or a ring system);-   each R⁸ is, independently, a C₁ to C₁₀ alkyl group;-   each R⁹ is, independently, a C₁ to C₁₀ alkyl group;-   each R¹⁰ is hydrogen;-   each R¹¹, R¹², and R¹³, is, independently, hydrogen or a substituted    or unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group;-   T is a bridging group, preferably represented by the formula R₂    ^(a)J, where J is a group 14 element (preferably C, Si, or Ge);-   each R^(a) is, independently, hydrogen, halogen or a C₁ to C₂₀    hydrocarbyl;-   two R^(a) can form a cyclic structure including aromatic, partially    saturated or saturated cyclic or fused ring system; and further    provided that any two adjacent R groups may form a fused ring or    multicenter fused ring system where the rings may be aromatic,    partially saturated or saturated; and-   further provided that any of adjacent R¹¹, R¹², and R¹³ groups may    form a fused ring or multicenter fused ring system where the rings    may be aromatic, partially saturated or saturated;

wherein

-   M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof;-   each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group; and-   each R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸    are, independently, hydrogen or a substituted or unsubstituted    hydrocarbyl group having from 1 to 8 carbon atoms, wherein the C₅ to    C₄₀ higher olefin is selected from butene, pentene, hexene, heptene,    octene, nonene, decene, undecene, dodecene, norbornene,    norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene,    cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene,    7-oxanorbornadiene, substituted derivatives thereof, and isomers    thereof-   7. A process for making the higher olefin copolymers of paragraphs 1    to 4, wherein the process comprises contacting:-   (i) from about 80 to about 99.9 mol % of at least one C₄ olefin,    preferably about 85 to about 99.9 mol %, more preferably about 90 to    about 99.9 mol % (preferably a mixed butene stream comprising    1-butene is used);-   (ii) from about 0.1 to about 20 mol % of propylene, preferably about    0.1 to about 15 mol %, more preferably about 0.1 to about 10 mol %;-   (iii) optionally, ethylene;-   wherein the contacting occurs in the presence of a catalyst system    comprising an activator and at least one metallocene compound    represented by at least one of the formulae:

where:

-   M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, and a combination thereof, (two X's may form a    part of a fused ring or a ring system);-   each Q is, independently carbon or a heteroatom;-   each R¹ is, independently, a C₁ to C₈ alkyl group, R¹ may the same    or different as R²;-   each R² is, independently, a C₁ to C₈ alkyl group;-   each R³ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group having from 1 to 8 carbon atoms,    provided however that at least three R³ groups are not hydrogen;-   each R⁴ is, independently, hydrogen or a substituted or    unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group;-   R⁵ is hydrogen or a C₁ to C₈ alkyl group;-   R⁶ is hydrogen or a C₁ to C₈ alkyl group;-   each R⁷ is, independently, hydrogen or a C₁ to C₈ alkyl group,    provided however that at least seven R⁷ groups are not hydrogen;-   R₂ ^(a)T is a bridging group, where T is a group 14 atom, preferably    C, Si, or Ge;-   each R^(a) is, independently, hydrogen, halogen or a C₁ to C₂₀    hydrocarbyl; and-   two R^(a) can form a cyclic structure including aromatic, partially    saturated or saturated cyclic or fused ring system; and further    provided that any two adjacent R groups may form a fused ring or    multicenter fused ring system where the rings may be aromatic,    partially saturated or saturated;

where:

-   M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halides, dienes, amines,    phosphines, ethers, and a combination thereof, (two X's may form a    part of a fused ring or a ring system);-   each R⁸ is, independently, a C₁ to C₁₀ alkyl group;-   each R⁹ is, independently, a C₁ to C₁₀ alkyl group;-   each R¹⁰ is hydrogen;-   each R¹¹, R¹², and R¹³, is, independently, hydrogen or a substituted    or unsubstituted hydrocarbyl group, a heteroatom or heteroatom    containing group;-   T is a bridging group, preferably represented by the formula R₂    ^(a)J, where J is a group 14 element (preferably C, Si, or Ge);-   each R^(a) is, independently, hydrogen, halogen or a C₁ to C₂₀    hydrocarbyl;-   two R^(a) can form a cyclic structure including aromatic, partially    saturated, or saturated cyclic or fused ring system; and further    provided that any two adjacent R groups may form a fused ring or    multicenter fused ring system where the rings may be aromatic,    partially saturated or saturated;-   further provided that any of adjacent R¹¹, R¹², and R¹³ groups may    form a fused ring or multicenter fused ring system where the rings    may be aromatic, partially saturated or saturated;

wherein

-   M is hafnium or zirconium;-   each X is, independently, selected from the group consisting of    hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides,    amides, alkoxides, sulfides, phosphides, halogens, dienes, amines,    phosphines, ethers, or a combination thereof;-   each R¹⁵ and R¹⁷ are, independently, a C₁ to C₈ alkyl group; and-   each R¹⁶, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸    are, independently, hydrogen or a substituted or unsubstituted    hydrocarbyl group having from 1 to 8 carbon atoms.-   8. The processes of paragraph 6 or 7, wherein the activator is a    bulky activator represented by the formula:

where:

-   each R₁ is, independently, a halide, preferably a fluoride;-   each R₂ is, independently, a halide, a C₆ to C₂₀ substituted    aromatic hydrocarbyl group or a siloxy group of the formula    —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or    hydrocarbylsilyl group, preferably a fluoride or a C₆ perfluorinated    aromatic hydrocarbyl group;-   each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl    group, or a siloxy group of the formula —O—Si—R_(a), where R_(a) is    a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group, preferably a    fluoride or a C₆ perfluorinated aromatic hydrocarbyl group;-   wherein L is a neutral Lewis base;-   H is hydrogen;-   (L-H)⁺ is a Bronsted acid;-   d is 1, 2, or 3;-   wherein the anion has a molecular weight of greater than 1020 g/mol;    and-   wherein at least three of the substituents on the B atom each have a    molecular volume of greater than 250 cubic Å, alternately greater    than 300 cubic Å, or alternately greater than 500 cubic Å.-   9. The process of paragraph 6 or 7, wherein the bulky activator is    at least one of: trimethylammonium    tetrakis(perfluoronaphthyl)borate, triethylammonium    tetrakis(perfluoronaphthyl)borate, tripropylammonium    tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium    tetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammonium    tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium    tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium    tetrakis(perfluoronaphthyl)borate,    N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,    tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium    tetrakis(perfluoronaphthyl)borate, triphenylphosphonium    tetrakis(perfluoronaphthyl)borate, triethylsilylium    tetrakis(perfluoronaphthyl)borate,    benzene(diazonium)tetrakis(perfluoronaphthyl)borate,    trimethylammonium tetrakis(perfluorobiphenyl)borate,    triethylammonium tetrakis(perfluorobiphenyl)borate,    tripropylammonium tetrakis(perfluorobiphenyl)borate,    tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,    tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate,    N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,    N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,    N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,    tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium    tetrakis(perfluorobiphenyl)borate, triphenylphosphonium    tetrakis(perfluorobiphenyl)borate, triethylsilylium    tetrakis(perfluorobiphenyl)borate,    benzene(diazonium)tetrakis(perfluorobiphenyl)borate,    [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B] (where Ph is phenyl and Me is    methyl).-   10. A composition comprising the higher olefin copolymers of    paragraphs 1 to 5 or made by the process of paragraphs 6 to 9,    preferably the composition is a lubricant blend.-   11. The use of the composition of paragraph 10 as a lubricant.

EXAMPLES

Product Characterization

Products were characterized by ¹H NMR, GPC, and ¹³C NMR as follows.

GPC

Mn, Mw, and Mz were measured by using a High Temperature Size ExclusionChromatograph (SEC, either from Waters Corporation or PolymerLaboratories), equipped with a differential refractive index detector(DRI). Experimental details, described in: T. Sun, P. Brant, R. R.Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp.6812-6820, (2001) and references therein, were used. Three PolymerLaboratories PLgel 10 mm Mixed-B columns were used. The nominal flowrate was 0.5 cm³/min, and the nominal injection volume was 300 μL. Thevarious transfer lines, columns and differential refractometer (the DRIdetector) were contained in an oven maintained at 135° C. Solvent forthe SEC experiment was prepared by dissolving 6 grams of butylatedhydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade1,2,4 trichlorobenzene (TCB). The TCB mixture was then filtered througha 0.7 μm glass pre-filter and subsequently through a 0.1 μm Teflonfilter. The TCB was then degassed with an online degasser beforeentering the SEC. Polymer solutions were prepared by placing dry polymerin a glass container, adding the desired amount of TCB, then heating themixture at 160° C. with continuous agitation for about 2 hours. Allquantities were measured gravimetrically. The TCB densities used toexpress the polymer concentration in mass/volume units were 1.463 g/mLat room temperature and 1.324 g/mL at 135° C. The injectionconcentration was from 1.0 to 2.0 mg/mL, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the injector were purged. Flow rate in theapparatus was then increased to 0.5 mL/minute, and the DRI was allowedto stabilize for 8 to 9 hours before injecting the first sample. Theconcentration, c, at each point in the chromatogram was calculated fromthe baseline-subtracted DRI signal, I_(DRI), using the followingequation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto, (dn/dc)=0.104 for propylene polymersand 0.1 otherwise. Units of parameters used throughout this descriptionof the SEC method are: concentration was expressed in g/cm³, molecularweight was expressed in g/mol, and intrinsic viscosity was expressed indL/g.

¹³C NMR

¹³C NMR data was collected at 120° C. at a ¹³C frequency of 100 MHz. A90 degree pulse, an acquisition time adjusted to give a digitalresolution between 0.1 and 0.12 Hz, at least a 10 second pulseacquisition delay time with continuous broadband proton decoupling usingswept square wave modulation without gating was employed during theentire acquisition period. The spectra were acquired with time averagingto provide a signal to noise level adequate to measure the signals ofinterest. Samples were dissolved in tetrachloroethane-d₂ atconcentrations between 10 wt % to 15 wt % prior to being inserted intothe spectrometer magnet.

Prior to data analysis spectra were referenced by setting the chemicalshift of the TCE solvent signal to 74.39 ppm.

Chain ends for quantization were identified using the signals shown inthe table below. N-butyl and n-propyl were not reported due to their lowabundance (less than 5%) relative to the chain ends shown in the tablebelow.

Chain End ¹³CNMR Chemical Shift P~i-Bu 23-5 to 25.5 and 25.8 to 26.3 ppmE~i-Bu 39.5 to 40.2 ppm P~Vinyl 41.5 to 43 ppm E~Vinyl 33.9 to 34.4 ppm

¹H NMR

¹H NMR data was collected at either room temperature or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹H frequency of 250 MHz, 400 MHz, or 500 MHz(for the purpose of the claims, a proton frequency of 400 mHz was used).Data was recorded using a maximum pulse width of 45° C., 8 secondsbetween pulses and signal averaging 120 transients. Spectral signalswere integrated and the number of unsaturation types per 1000 carbonswas calculated by multiplying the different groups by 1000 and dividingthe result by the total number of carbons. Mn was calculated by dividingthe total number of unsaturated species into 14,000, and has units ofg/mol.

The chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Unsaturation Type Region (ppm) Number of hydrogens per structure Vinyl4.95-5.10 2 Vinylidene (VYD) 4.70-4.84 2 Vinylene 5.31-5.55 2Trisubstituted 5.11-5.30 1Viscosity

Viscosity was measured using a Brookfield Digital Viscometer.

Metallocenes Used in Examples

The following metallocenes were used in the examples below.

Metallocene Structure A (Comparative)

B (Comparative)

C (Comparative)

D

E

F

G

Activators Used

The following activators were used in the examples below.

Activator Chemical Name IDimethylaniliniumtetrakis(pentafluorophenyl)borate IIDimethylaniliniumtetrakis(perfluorobiphenyl)borate IIIDimethylaniliniumtetrakis(perfluoronaphthyl)boratePolymerization Conditions for Examples 1-6

Polymerization grade propylene was used and further purified by passingit through a series of columns: 2250 cc Oxyclear cylinder from Labelear(Oakland, Calif.), followed by a 2250 cc column packed with dried 3 Åmole sieves purchased from Aldrich Chemical Company (St. Louis, Mich.),two 500 cc columns packed with dried 5 Å mole sieves purchased fromAldrich Chemical Company, one 500 cc column packed with ALCOA SelexsorbCD (7×14 mesh) purchased from Coastal Chemical Company (Abbeville, La.),and one 500 cc column packed with ALCOA Selexsorb COS (7×14 mesh)purchased from Coastal Chemical Company.

Polymerization grade hexanes was further purified by passing it througha series of columns: two 500 cc Oxyclear cylinders from Labelearfollowed by two 500 cc columns packed with dried 3 Å mole sievespurchased from Aldrich Chemical Company, and two 500 cc columns packedwith dried 5 Å mole sieves purchased from Aldrich Chemical Company, andused.

Scavengers and Co-catalysts

Triisobutyl aluminum (TIBAL) was obtained from Akzo Chemicals, Inc.(Chicago, Ill.) and used without further purification. Tri n-octylaluminum (TNOAL) was obtained from Akzo Chemicals, Inc. and used withoutfurther purification.

Reactor Description and Preparation

Polymerizations were conducted in an inert atmosphere (N₂) drybox using48 Cell Parallel Pressure Reactors (PPR) equipped with external heatersfor temperature control, glass inserts (internal volume of reactor=22.5mL), septum inlets, regulated supply of nitrogen, propylene, andequipped with disposable PEEK (PolyEtherEtherKetone) mechanical stirrers(800 RPM). The PPRs were prepared for polymerization by purging with drynitrogen at 150° C. for 5 hours and then at 25° C. for 5 hours.

Example 1 Decene-Propylene, Hexene-Propylene, andDecene-Hexene-Propylene Polymerizations with Metallocenes E and F

The reactor was prepared as described above, and then charged with1-decene and/or 1-hexene. The reactors were heated to 25° C. andpropylene was then charged to the reactor. A solution ofscavenger/co-catalyst at process temperature and pressure was next addedto the reactors via syringe. The reactors were heated to processtemperature (85° C.) and stirred at 800 RPM.

Metallocene catalysts were mixed with the activator and stirred intoluene at ambient temperature and pressure and added to the reactors(at process temperature and pressure) via syringe as a solution toinitiate polymerization. Because the solutions are added via syringe, ahexanes solution is also injected via the same syringe following theiraddition to insure that minimal solution is remaining in the syringe.This procedure is applied after the addition of thescavenger/co-catalyst solution as well as the catalyst solution.

Propylene was allowed to enter the reactors to a desired pressurethrough the use of regulators and allowed to drop during thepolymerization. No pressure control was employed during the run. Reactortemperatures were monitored and typically maintained within a +/−1° C.temperature range. Polymerizations were quenched by the addition ofapproximately 50 psi (345 kPa) delta of Industrial Grade Air forapproximately 60 seconds. The polymerizations were quenched after thedesired polymerization time. The reactors were cooled and vented. Thepolymer was isolated after the remaining reaction components wereremoved in-vacuo. Yields reported include total weight of polymer andresidual catalyst. Yields are listed in Table 1A, below.

TABLE 1A Polymerization to Produce Copolymers and Terpolymers ofPropylene and Decene and/or Hexene Temperature = 85° C.; Reaction Time =60 min; [Metallocene] = [activator] = 1.6 × 10⁻⁵ M Concentration, mol/LRun Metallocene Activator [C₃] [C₆] [C₁₀] Yield, mg A1 E III 1.91 3.33 0970.4 A2 E III 1.53 3.33 0 800.4 A3 E III 1.15 3.33 0 510.8 A4 E III0.77 3.33 0 332.5 A5 E III 0.38 3.33 0 296.1 A6 E III 0 3.33 0 146.5 B1E III 1.91 1.66 1.06 1092.7 B2 E III 1.53 1.66 1.06 708.4 B3 E III 1.151.66 1.06 520.9 B4 E III 0.77 1.66 1.06 523 B5 E III 0.38 1.66 1.06422.2 B6 E III ca 0 1.66 1.06 273.5 C1 E III 1.91 3.33 0 872.9 C2 E III1.53 3.33 0 681.6 C3 E III 1.15 3.33 0 616 C4 E III 0.77 3.33 0 388.7 C5E III 0.38 3.33 0 334.7 C6 E III 0 3.33 0 240.8 D1 E III 1.91 1.66 1.061049.7 D2 E III 1.53 1.66 1.06 773.4 D3 E III 1.15 1.66 1.06 578 D4 EIII 0.77 1.66 1.06 449.2 D5 E III 0.38 1.66 1.06 426.2 D6 E III 0 1.661.06 305.7 E1 F II 1.91 3.33 0 676.6 E2 F II 1.53 3.33 0 395.9 E3 F II1.15 3.33 0 355.4 E4 F II 0.77 3.33 0 192.5 E5 F II 0.38 3.33 0 135.1 E6F II 0 3.33 0 50.7 F1 F II 1.91 1.66 1.06 837.9 F2 F II 1.53 1.66 1.06498.3 F3 F II 1.15 1.66 1.06 417.2 F4 F II 0.77 1.66 1.06 309.6 F5 F II0.38 1.66 1.06 200.8 F6 F II 0 1.66 1.06 76.8 G1 F II 1.91 3.33 0 634.7G2 F II 1.53 3.33 0 326.4 G3 F II 1.15 3.33 0 307.7 G4 F II 0.77 3.33 0211.5 G5 F II 0.38 3.33 0 140.2 G6 F II 0 3.33 0 15.9 H1 F II 1.91 1.661.06 729.4 H2 F II 1.53 1.66 1.06 534.4 H3 F II 1.15 1.66 1.06 459.7 H4F II 0.77 1.66 1.06 238 H5 F II 0.38 1.66 1.06 174.3 H6 F II 0 1.66 1.0688

Data from the analysis of some of the cell products is shown in theTable 2B, below.

TABLE 1B Characterization Data for Copolymers and Terpolymers OfPropylene and Decene and/or Hexene mol % mol % mol % Mn mol % C₆ Runvinyls vinylidene Others (¹HNMR) and/or C₁₀* A1 92.3 6.3 1.4 1737 47.9A2 87.5 8.6 3.9 1664 55.4 A5 75.4 15.9 8.7 1980 84.7 B1 89.1 8.2 2.71614  49.0* B3 85.7 10.2 4.1 2206  64.5* B6 61.9 26.2 11.9 3744  97.4*E1 75.4 19.9 4.7 2091 41.5 E4 57.5 29.4 13.1 2744 72.5 F1 73.7 21.4 4.92067 44*  F3 68 25.2 6.8 2603  52.8* KEY: *Methyls from hexene anddecene not resolved enough in ¹H NMR to quantify separately. This valueis the sum of both.

Runs A1, A2, and A5 are copolymerizations of propylene and hexene, usingmetallocene E and activator III. Runs E1 and E4 are copolymerizations ofpropylene and hexene, using metallocene F and activator II. Theinventors observed that with increasing propylene content there was aconcurrent increase in % vinyls. Also, with decreasing propylene feed,there was an observed increase in Mn, presumably through incorporationof more of the higher molecular weight hexene.

Runs B1, B3, and B6 are terpolymerizations of propylene, hexene, anddecene, using metallocene E and activator III. Runs F1 and F3 areterpolymerizations of propylene, hexene, and decene, using metallocene Fand activator II. It was similarly observed that with increasingpropylene content, there was a concurrent increase in % vinyls. Also,with decreasing propylene feed, there was an observed increase in Mn,presumably through incorporation of more of the higher molecular weighthexene and decene.

Example 2 Octene-propylene Copolymerizations with Metallocenes E and G

Solution runs were performed as follows: propylene was first added tothe reaction cell, then octene and isohexane was added such that thetotal solution volume was 5.0 mL. TNOAL was used as scavenger at aconcentration of 1 M. A solution of activator III in toluene was addedfirst followed by a solution of the metallocene E or F such that theactivator to metallocene ratio was 1:1. The cells were heated to 85° C.and the reaction proceeded for 1 hour. The reaction was quenched withair and unreacted monomers were removed in vacuo. Analysis of some ofthe cell products are listed in Table 2B.

TABLE 2A Octene-Propylene Copolymerizations. Run time = 60 minutes;Activator to metallocene ratio = 1:1; Reaction temperature = 85° C.;TNOAL = 1.2 × 10−4 mol/L. Ac- tiva- [C₃], [C₈], [metallocene], Yield,Run Metallocene tor mol/L mol/L mol/L mg A1 E III 1.91 1.28  8.0 × 10−6486 A2 E III 1.91 1.66  8.0 × 10−6 629 A3 E III 1.2 2.04  8.0 × 10−6 401A4 E III 1.2 2.43  8.0 × 10−6 579 A5 E III 0.48 2.81  8.0 × 10−6 525 A6E III 0.48 3.19  8.0 × 10−6 388 B1 E III 1.91 1.28  8.0 × 10−6 506 B2 EIII 1.91 1.66  8.0 × 10−6 648 B3 E III 1.2 2.04  8.0 × 10−6 577 B4 E III1.2 2.43  8.0 × 10−6 674 B5 E III 0.48 2.81  8.0 × 10−6 530 B6 E III0.48 3.19  8.0 × 10−6 561 C1 G III 1.91 1.28  8.0 × 10−6 378 C2 G III1.91 1.66  8.0 × 10−6 443 C3 G III 1.2 2.04  8.0 × 10−6 443 C4 G III 1.22.43  8.0 × 10−6 603 C5 G III 0.48 2.81  8.0 × 10−6 638 C6 G III 0.483.19  8.0 × 10−6 597 D1 G III 1.91 1.28  8.0 × 10−6 380 D2 G III 1.911.66  8.0 × 10−6 522 D3 G III 1.2 2.04  8.0 × 10−6 470 D4 G III 1.2 2.43 8.0 × 10−6 503 D5 G III 0.48 2.81  8.0 × 10−6 625 D6 G III 0.48 3.19 8.0 × 10−6 578 E1 E III 1.91 1.28 1.60 × 10−5 693 E2 E III 1.91 1.661.60 × 10−5 960 E3 E III 1.2 2.04 1.60 × 10−5 996 E4 E III 1.2 2.43 1.60× 10−5 1,176 E5 E III 0.48 2.81 1.60 × 10−5 1,081 E6 E III 0.48 3.191.60 × 10−5 1,079 F1 E III 1.91 1.28 1.60 × 10−5 727 F2 E III 1.91 1.661.60 × 10−5 972 F3 E III 1.2 2.04 1.60 × 10−5 945 F4 E III 1.2 2.43 1.60× 10−5 1,141 F5 E III 0.48 2.81 1.60 × 10−5 954 F6 E III 0.48 3.19 1.60× 10−5 1,126 G1 F III 1.91 1.28 1.60 × 10−5 630 G2 G III 1.91 1.66 1.60× 10−5 751 G3 G III 1.2 2.04 1.60 × 10−5 914 G4 G III 1.2 2.43 1.60 ×10−5 1,097 G5 G III 0.48 2.81 1.60 × 10−5 1,231 G6 G III 0.48 3.19 1.60× 10−5 1,230 H1 G III 1.91 1.28 1.60 × 10−5 497 H2 G III 1.91 1.66 1.60× 10−5 637 H3 G III 1.2 2.04 1.60 × 10−5 589 H4 G III 1.2 2.43 1.60 ×10−5 888 H5 G III 0.48 2.81 1.60 × 10−5 1,146 H6 G III 0.48 3.19 1.60 ×10−5 1,319

Data from the analysis of some of the cell products is shown in theTable 2B, below.

TABLE 2B Data for C₈/C₃ copolymers. mol % C₈ mol % C₈ GPC isobutyl tomol % mol % mol % Mn by by by ¹³C Mw/ vinyl Run vinyls VYD Others ¹HNMR¹H NMR NMR Mn Mn integration A1 94.9 3.9 1.2 1,261 36.9 36.4 851 2.10.60 B1 92.8 5.9 1.3 1,287 39 — 1151 1.7 — B3 91 6.9 2.1 1,769 53 — 10742.2 — B6 91 6.1 2.9 3,147 71 — 1601 2.2 — C1 92 8 0 411 60 62.3 288 1.40.68 C3 92 8 0 400 72 — — — — C6 81 19 0 764 83 — — — — VYD = vinylidene

Example 3 Decene-Propylene Polymerization (Comparison of Metallocene Ewith Metallocene D)

Run time was 60 minutes; Activator to metallocene ratio=1:1; Reactiontemperature was 85° C.; TNOAL=1.2×10⁻⁴ mol/L.

TABLE 3A Comparison of Metallocene E with Metallocene D Concentration,mol/L Temperature, Yield, Run Metallocene Activator [C₃] [C₁₀] ° C. mgA1 E I 0.057 2.33 85 474 A2 E I 0.057 2.33 85 602 A3 E I 0.057 2.33 95507 A4 E I 0.057 2.33 95 506 A5 E I 0.057 2.33 105 523 A6 E I 0.057 2.33104.9 545 B1 D I 0.057 2.33 85 148 B2 D I 0.057 2.33 84.9 209 B3 D I0.057 2.33 95.1 142 B4 D I 0.057 2.33 95 106 B5 D I 0.057 2.33 104.9 101B6 D I 0.057 2.33 105 76 C1 E III 0.057 2.33 85 303 C2 E III 0.057 2.3385.1 329 C3 E III 0.057 2.33 95 316 C4 E III 0.057 2.33 95 233 C5 E III0.057 2.33 105.2 259 C6 E III 0.057 2.33 105.1 191 D1 D III 0.057 2.3385.1 174 D2 D III 0.057 2.33 85 239 D3 D III 0.057 2.33 95 88 D4 D III0.057 2.33 95.1 53 D5 D III 0.057 2.33 105.1 24 II D III 0.057 2.33105.1 21 E1 E I 0.96 2.33 85 1144 E2 E I 0.96 2.33 84.9 1252 E3 E I 0.962.33 95 1056 E4 E I 0.96 2.33 95 991 E5 E I 0.96 2.33 105.1 846 E6 E I0.96 2.33 104.9 750 F1 D I 0.96 2.33 85 127 F2 D I 0.96 2.33 85.2 150 F3D I 0.96 2.33 94.9 90 F4 D I 0.96 2.33 94.9 98 F5 D I 0.96 2.33 105 93F6 D I 0.96 2.33 105.1 50 G1 E III 0.96 2.33 85 820 G2 E III 0.96 2.3384.9 680 G3 E III 0.96 2.33 95 601 G4 E III 0.96 2.33 94.9 481 G5 E III0.96 2.33 105 377 G6 E III 0.96 2.33 105.2 359 H1 D III 0.96 2.33 85 170H2 D III 0.96 2.33 85 154 H3 D III 0.96 2.33 94.9 100 H4 D III 0.96 2.3395.1 72 H5 D III 0.96 2.33 105.1 53 H6 D III 0.96 2.33 104.8 44

Data from the analysis of some of the cell products is shown in theTable 3B, below.

TABLE 3B Data for Comparison of Metallocene E with Metallocene D mol %C₈ mol % C₈ isobutyl to mol % mol % mol % Mn by by ¹H by ¹³C vinyl Runvinyls vinylidenes Others ¹HNMR NMR NMR integration A1 52.9 41.2 5.92224 90.7 — — A6 39.9 51 9.1 1309 98.5 — — B1 60.3 38.2 1.5 1300 91.8 —— B6 41.7 57.1 1.2 890 93.7 — — G1 85.8 11.3 2.9 1800 66.7 — — H1 87.911.5 0.6 690 69.2 — — H2 89 10.7 0.3 682 77.5 78.9 28.2

Example 4 Decene-Propylene Polymerization (Comparison of Metallocene Ewith Comparative Metallocenes A, B, & C)

Non-inventive metallocenes A, B, and C were compared with Metallocene Eof the present invention. Run time was 60 minutes; Activator tometallocene ratio=1:1; Reaction temperature was 85° C.; TNOAL=1.2×10⁻⁴mol/L.

TABLE 4A Comparison of Metallocene E with Comparative Metallocenes. RunMetallocene Activator [C₃], mol/L [C₁₀], mol/L Yield, mg A1 E III 1.91.06 608 A2 E III 1.9 1.38 542 A3 E III 1.2 1.69 573 A4 E III 1.2 2.01698 A5 E III 0.48 2.33 348 A6 E III 0.48 2.65 39 B1 B III 1.9 1.06 254B2 B III 1.9 1.38 426 B3 B III 1.2 1.69 500 B4 B III 1.2 2.01 106 B5 BIII 0.48 2.33 695 B6 B III 0.48 2.65 8 C1 A III 1.9 1.06 288 C2 A III1.9 1.38 325 C3 A III 1.2 1.69 222 C4 A III 1.2 2.01 147 C5 A III 0.482.33 93 C6 A III 0.48 2.65 169 D1 C III 1.9 1.06 590 D2 C III 1.9 1.38447 D3 C III 1.2 1.69 287 D4 C III 1.2 2.01 38 D5 C III 0.48 2.33 128 D6C III 0.48 2.65 84 E1 E I 1.9 1.06 817 E2 E I 1.9 1.38 1041 E3 E I 1.21.69 1005 E4 E I 1.2 2.01 693 E5 E I 0.48 2.33 972 E6 E I 0.48 2.65 481F1 B I 1.9 1.06 230 F2 B I 1.9 1.38 292 F3 B I 1.2 1.69 331 F4 B I 1.22.01 359 F5 B I 0.48 2.33 521 F6 B I 0.48 2.65 61 G1 A I 1.9 1.06 476 G2A I 1.9 1.38 494 G3 A I 1.2 1.69 412 G4 A I 1.2 2.01 349 G5 A I 0.482.33 220 G6 A I 0.48 2.65 175 H1 C I 1.9 1.06 858 H2 C I 1.9 1.38 872 H3C I 1.2 1.69 959 H4 C I 1.2 2.01 1191 H5 C I 0.48 2.33 891 H6 C I 0.482.65 806

Data from the analysis of some of the cell products is shown in theTable 4B, below.

TABLE 4B Data for Comparison of Metallocene E with ComparativeMetallocenes mol % mol % mol % Mn by % GPC-DRI Run MCN Activator vinylsVYD Others ¹HNMR C₁₀ Mn Mw/Mn A1 E III 97 3 0 1836 46 1151 2   A5 E III86.8 10.2 3 2478 57.1 — — B1 B III 9.3 61.7 29 7671 33.5 5293 1.9 B5 BIII 8.8 63.5 27.7 7180 66.8 — — C1 A III 18 3.7 78.3 6963 53.3 5499 2.1C5 A III 8.2 3.2 88.6 5791 71.3 — — D1 C III 0 63 37 5867 41.6 3597 2  D5 C III 1.7 68.4 70.1 4712 73.3 — — E1 E I 77.5 20 2.5 1281 34.6 — — E5E I 67.9 28.8 3.3 2224 60.8 — — F1 B I 3 82.9 14.1 2095 42.2 — — F5 B I3.3 72.3 24.4 2692 74.1 — — G1 A I 27.8 14.9 57.3 5705 33.9 — — G5 A I 99.6 81.4 5460 72.2 — — H1 C I 1.4 86.9 11.7 685 40 — — H5 C I 0.3 85.114.6 1241 70 — — KEY: MCN = metallocene, VYD = vinylidene

Example 5 Comparison of Activators I to III

Run time was varied, as indicated in Table 6; Activator to metalloceneratio=1:1; Reaction temperature was 85° C.; MCN=5×10⁻⁵ mol/L;TNOAL=1.2×10⁻⁴ mol/L. Total solution volume was 5 mLs.

TABLE 5A Comparison Of Activators I to III Metallocene Run (MCN)Activator [C₃], mol/L Run Time, s Yield, mg A1 E I 1.4 300.7 62.7 A2 E I1.4 216.1 87.5 A3 E III 1.4 298.3 80 A4 E III 1.4 301.3 82.1 A5 E II 1.4303 79.6 A6 E II 1.4 286.8 78 B1 G I 1.4 211.7 103.5 B2 G I 1.4 219.5107.3 B3 G III 1.4 217.8 99.1 B4 G III 1.4 213.9 107.4 B5 G II 1.4 243.6104.9 B6 G II 1.4 300.7 92.9 C1 A I 1.4 71.3 163.4 C2 A I 1.4 71.6 170C3 A III 1.4 94.5 157.3 C4 A III 1.4 80.8 145.5 C5 A II 1.4 99.1 148.5C6 A II 1.4 103.7 154.9 D1 G I 1.4 61.1 190.9 D2 G I 1.4 60.2 197.9 D3 GIII 1.4 76.2 166.1 D4 G III 1.4 74.8 178.9 D5 G II 1.4 117.7 155 D6 G II1.4 115.9 156 E1 E I 2.9 198 125.4 E2 E I 2.9 141.5 144.7 E3 E III 2.9144.7 137.3 E4 E III 2.9 171 133.4 E5 E II 2.9 189.1 135.5 E6 E II 2.9175.2 121.5 F1 G I 2.9 138.7 147.6 F2 G I 2.9 173.2 141.9 F3 G III 2.9161.3 150.4 F4 G III 2.9 125.2 165.4 F5 G II 2.9 127.9 163 F6 G II 2.9157.4 139.4 G1 A I 2.9 55.4 265.5 G2 A I 2.9 56.1 271.5 G3 A III 2.975.7 245.2 G4 A III 2.9 90.5 234 G5 A II 2.9 80.5 233.4 G6 A II 2.9 81.8240.7 H1 G I 2.9 37 296.7 H2 G I 2.9 45.4 326.9 H3 G III 2.9 54.2 319.3H4 G III 2.9 49 294.6 H5 G II 2.9 72.2 281.3 H6 G II 2.9 78.6 276.5

Data from the analysis of some of the cell products is shown in theTable 5B, below.

TABLE 5B Data For Comparison Of Activators I to III mol % mol % Mn MnRun MCN ACT Yield g Vinyls VYD (¹HNMR) (GPC) Mw/Mn (GPC) A1 E I 0.063 8812 655 — — A2 E I — — — — 1137 2.2 A3 E III 0.08 98.6 1.4 642 1072 2.9A5 E II 0.08 99.2 0.8 786 857 1.6 B1 G I 0.104 52.2 47.8 683 745 1.4 B3G III 0.099 92.4 7.6 1018 4416 2.3 B5 G II 0.105 95.7 4.3 1073 1079 1.7C1 A I 0.163 70.8 29.2 4806 2775 3.1 C3 A III 0.157 91.2 6.3 7441 57542.2 C5 A II 0.149 85.5 12.8 7119 6326 2.1 D1 G I 0.191 31.8 62.5 16,71213,597 2.6 D3 G III 0.166 66.1 33.8 32,186 36,789 2.4 D5 G II 0.155 57.441.3 38,166 34,217 2.3 G1 A I 0.266 71.5 27.2 4424 — — G3 A III 0.24591.3 5.9 7762 — — G5 A II 0.233 81.6 13.5 9277 — — KEY: MCN =metallocene, ACT = activator, VYD = vinylidene

Examples 6 & 7 Polymerization Conditions

Anhydrous toluene was purchased from Sigma Aldrich (Chicago, Ill.) andwas further dried over 4 Å molecular sieves under an inert atmosphere.

In the dry box, 10 mLs of toluene was used to dissolve a 1/1.1equivalent ratio of metallocene/activator. The solution was stirred for30 minutes. Five mLs of the solution was then transferred to thecatalyst charger.

Higher olefin comonomer (5 g) was dissolved in 5 mLs of toluene and wascharged into a syringe. Scavenger (TIBAL) (0.5 mLs of 1 M solution) wascharged into a syringe.

Preparation of Reactor

The 2 L Zipper Autoclave reactor was baked at 120° C. for 1 hour under anitrogen purge. The reactor was then cooled to room temperature undercontinuous nitrogen purge. Feed lines for isohexane and propylene werelinked to the reactor lines, and the feed streams passed through amolecular sieve dryer (4 Å molecular sieves) prior to filling into sightglasses.

Reactor Run Procedure

The catalyst charger containing the metallocene/activator solution wasattached to the reactor at an entry port. A high pressure nitrogen linewas attached to the charger to discharge the catalyst into the reactorat the appropriate time.

The vent line to the reactor was closed. Using less than one pound ofpressure purging out of the reactor, the higher olefin comonomer wassyringed into the bottom of the reactor, using a second port. Then,using the same port, the scavenger was charged into the reactor, and theport closed. The nitrogen line to the reactor was closed. Isohexane wasadded to the reactor, followed by of propylene. The agitator was startedat 800 rpm, and the reactor heated to the required process temperature.

Once the reactor pressure was stable at the required processtemperature, the catalyst was pushed into the reactor with a nitrogenpressure 40 lbs above reactor pressure. The charger port was closed offfrom the reactor and the reactor software turned on to monitor pressureloss and temperature change in the reactor. The reactor was run for thedesired run time. Once the software had been stopped, the reactor wascooled to RT, and the pressure vented. The solution of product andsolvents was poured out of the reactor into a glass beaker and thesolvents removed by nitrogen purge.

Example 6 Copolymerization of Hexene and Propylene for Viscosity Studies

Higher olefin (hexene/propylene) copolymers were made under theconditions shown in Table 7A. In the dry box, 10 mLs of toluene was usedto dissolve a 1/1.1 equivalent ratio of Metallocene E/Activator III(10.7 mg/24.1 mg). TIBAL (0.5 mLs of 1 M solution) was charged into asyringe. Volume of isohexane used was 600 mL. Run conditions are shownin Table 6A, below.

TABLE 6A Hexene/Propylene Copolymers Run Run Mn by ¹H C₃, C₆, temp,time, Polymer Activity, NMR Run # mLs mLs C. min yield, g gP/gcat · hr(g/mol) 1 200 100 80 30 149 85143 1700 2 200 100 60 16 126 135000 4500

The viscosities of the VT-HO C₆/C₃ copolymers from Runs 1 and 2 werecompared with VT-HO atactic C₃ homopolymers and are reported in Table 6Bbelow and depicted in FIG. 1.

TABLE 6B Comparative Viscosities of C₃ Homopolymers and C₆/C₃ CopolymersMn by ¹HNMR Temperature Torque Viscosity Polymer Type (g/mol) (° C.) (%)(cP) C₃ Homopolymer 1,540 40 44.2 5,525 50 17 2,125 60 7.7 962.5 C₃/C₆Copolymer 1,700 39.6 50.7 5,387 49.3 20.7 2,537 60 46.3 1,100 C₃Homopolymer 6,542 50 78.5 392,000 60 23.6 117,000 70 8.4 42,000 C₃/C₆Copolymer 4,500 60 63.6 31,800 70 53.6 13,400 80 25.8 6,425

Example 7 Copolymerization of Norbornene and Propylene

Preparation of Catalyst, Norbornene, and Scavenger

In the dry box, 10 mL of toluene was used to dissolve a 1/1.1 equivalentratio of Metallocene G/Activator III (13.7 mg/30.9 mg) respectively. Thesolution was stirred for 30 minutes. Five mLs of the solution (3 mg) wasthen transferred to the catalyst charger. Norbornene (5 g) was dissolvedin 5 mLs of toluene was charged into a syringe. TIBAL (0.5 mLs of 1 Msolution) was charged into a syringe. Volume of isohexane used was 300mLs.

TABLE 7 Norbornene/Propylene Copolymers C₃, NB, Run temp, Run time,Polymer Run # mLs mLs ° C. min yield, g 1 60 100 60 33 0.220

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents, related applications, and/or testing proceduresto the extent they are not inconsistent with this text, provided howeverthat any priority document not named in the initially filed applicationor filing documents is NOT incorporated by reference herein. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law. Likewise whenever a composition, an element or a groupof elements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

1. A higher olefin copolymer having an Mn of 300 g/mol or more (measuredby ¹H NMR) comprising: (i) from about 20 to about 99.9 mol % of at leastone C₅ to C₄₀ higher olefin; and (ii) from about 0.1 to about 80 mol %of propylene; wherein the higher olefin copolymer has at least 40% allylchain ends.
 2. The higher olefin copolymer of claim 1, wherein thecopolymer has an isobutyl chain end to allyl chain end ratio of lessthan 0.7:1.
 3. The higher olefin copolymer of claim 1, wherein thecopolymer has an allyl chain end to vinylidene chain end ratio of morethan 2:1.
 4. The higher olefin copolymer of claim 1, wherein the C₅ toC₄₀ higher olefin is selected from pentene, hexene, heptene, octene,nonene, decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof.
 5. The higherolefin copolymer of claim 1, wherein the higher olefin copolymer has aviscosity at 60° C. of greater than 1000 cP.
 6. A composition comprisingthe higher olefin copolymer of claim
 1. 7. A higher olefin copolymerhaving an Mn of 300 g/mol or more (measured by ¹H NMR) comprising: (i)from about 80 to about 99.9 mol % of at least one C₄ olefin; (ii) fromabout 0.1 to about 20 mol % of propylene; and wherein the higher olefincopolymer has at least 40% allyl chain ends.
 8. The higher olefincopolymer of claim 7, wherein the copolymer has an isobutyl chain end toallyl chain end ratio of less than 0.7:1.
 9. The higher olefin copolymerof claim 7, wherein the copolymer has an allyl chain end to vinylidenechain end ratio of more than 2:1.
 10. The higher olefin copolymer ofclaim 7, wherein the higher olefin copolymer comprises at least 50 wt %,based upon the weight of the copolymer composition, of olefins having atleast 36 carbon atoms, as measured by ¹H NMR, assuming one unsaturationper chain.
 11. A composition comprising the higher olefin copolymer ofclaim 7.